P.1 

OAR Box 1128 

Prepped by Ollie Stewart 

Document Number: 

20) 11-1-198 

Docket Number: 

A-83-22 

Printed 4/21/2008 11:07:11 AM Sheet 20 of 198 
The highest concentrations and a major portion of 

the stored lead were associated with the urban compartment and ares adjacent to high-use rural roads. 

These areas should be monitored in the future to 

detect changes in lead storage and concentrations 

with time and with additional lead input, to determine if toxic levels are reached. 

Insect food chains and insectivorous birds should 

also be closely monitored in high-lead-input areas. 

Aquatic systems should receive closer examination 

in the future, as sediments are major metal reservoirs. 

REFERENCES 

I. O. L. RoHa, A. Ctnker, ] . Melta. Bid B. B Ewkis. J. Environ. Syi. X'): 3 » (1972). 

1 E. N. Canfwril, E S. Jacobs. W. O. Lunz. Jr.. n d V. B. 

Liberi. Cycling and Control of Metals. 95 (1972). 

3. U. S. FuMc Health Service. Pubiicatkn No. 999-AP-l} 

(I9S5). 

4. L. B. Tcpper and L. S. Levin. UnhwrsHy of Cincinnati. College of MedTcme, Department of Environmental Health 

(I9T2). 

3. T. J. Kneip. M. Eiaenbud. C. D. Strehlow. and P. C. Freudenthal. J. Air Pollut. Com. An. 20:144 (1970). 

«. J. M. CohKci. C. R. Begeman. and K. Kinder. J. Air PoOU. 

Contr. All. I* 233 (1M9). 

7. H. R. Bowman. J. G. Conway, and P. Aiara. Environ. Sci. 

Techncl.d: 53>(I972). 

134 

P. R. Harrison. W. R. Mstson, and J. W. Winchester. *,„ _ 

Environ. .5.613(1971). 

J. L. Hudson, J. J. Stukel. and R. L. Solomon. Annua, bviron. (1975 in preta). 

A. L. Page. T. J. Omle. and M. S. JoaM. HOganfia. 41-1 

(1971). 

H. S. Molto, R. H. Bainei, D. M. CMlko. and C. K. How 

Environ. Sci. Technd. 4:231 11970). 

A. Ruhling and O. Tyler. Bot. Notiser. 121:321 (196(1. 

A. Suchdoller. Ber. der SclweUeiischen Botannchen OeaaVachafl. 77:266(1967). 

G. C. Marten and P. B. Hammond. Agron. J. 3R- 553 (1966). 

A. Koike and K. Riebaflach. Natunvissemchaften. SI: XI 

(1964). 

H. L. Cannon and J. M. Bowles. Science. (37:763 (1977). 

A. Haney, J.A. Carlton. G.L. Rolfe. RI. Acad. Sci. 67 nv 

323(1974). 

O.L. Rolfe. For. Sci. 2uJ): 283 (1974). 

H.W. Kreuger. N. W. Projecf 72-3. Kmiger Entctvrnes, 

Cambridge, MA (1972). 

P.W. Price, BJ. Rathckc. and D.A. Oentry. Environ. Entoroot 3(3): 370(1974). 

B. P. Hunt. Mich. Dept. Coneerv. BnO. ban. Fish. Res. 4 I 

(1953). 

M. J. CaJdweO and R. V. Bovbjerg. Proc. Iowa Acad. Sd. 7i 

461(1969). 

C. L. Toner. Ohio J. Sd. 22 41 (1921). 

N. H. Stewart. Bull. U. S. Bur. Fun. 42 147(1926). 

W. C. Kraatl. Ohio J. Sd. 29(2): >6 (1928). 

9. A. Forbes and R. B. Richardson. Minors Laboratory of 

National History Survey, 2nd ed.(1920). 

C. L. Huobs and G. P. Cooper. Cranbrook Inst. Sci. Bull. I 

I (1936). 

J. S. Dinsmcre. Proc. lows Acad. Sd. 69. 296 (1962). 

R. D. Hoyt. Amer. Midi. Nat. W(l>: 226 (1970). 

S. A. Forbes. Bull. Bl. St. Lab. Nat. Hist. 1(3): llOSn). 

CHAPTER 

TRANSPORT AND DISTRIBUTION FROM MINING 

MILLING, AND SMELTING OPERATIONS IN A FOREST 

ECOSYSTEM 

J. Chv/et Jennett*, Bobby O. Whuon, M » H. Lomhy. and Kmftnfcr 

Department of Civil Engineerint 

Umvexiity of Missouri-Ron* 

Ernst Bolter 

Dcpirtinent of Qeolofy 

University of MbsourlRotli 

Ddbtrt D. HesuphSJ 

ProsYUti Director - Bin u\jorii**ntM Trice Suostinoes Resesrcb Center 

University of Mluouri-Cohiinbia 

NdrriL-CWe 

Division of Life Science 

University of Minoari-RoOa 

WtUhmH. Tranfer 

Dt|iai t merit of Elcctiicu Enfnieenna 

Umvenity of Missouri-RoOt 

lillf II 

VM I 3 1992 

EPA A,R DOCKET 

HISTORY AND DEVELOPMENT 

Lead was first discovered in Missouri by French 

fevdopers in 1701 and mined from shallow surface 

fcposits as early as 1720. (t] Since that time production has increased gradually, with most of it coming 

torn the Old Lead Belt in Madison and St. Francis 

counties, both in southeast Missouri. Explorations 

by the St. Joe Lead Co. (now St. Joe Minerals 

Corp.) discovered new detoits in Washington County 

nd led to development of the Indian Creek Division 

Mine in 1953. (These mines are just north of, and 

not considered to be part of, the Viburnum Trend.) 

In 1955 St. Joe Co. verified initial lead ore dis-

, emeries near Viburnum. This rich lead-zinc deposit 

otends approximately 40 mi due south from Viburn-

|*n and is more or less continuously mineralized 

from a width of a few hundred to a few thousand 

licet. The lead-zinc ore varies from low to an ex-

| trwrdinarily high grade and has proven to be of 

met, higher quality than was forecast in the initial 

operation program. Both lead and zinc are primariTiamtty chairman. Heparin*!., of Civil Engineering. Syracuse 

Wversity. 

ly recovered as coproducts of (he lead ore. f2] This 

new lead-rich area was named the Viburnum 

Trend or New Lead Belt of Missouri. The geographical location is shown in figure 7-1 along with the 

location of mines and one smelter. Most of this 

major mineral discovery is on federal land (Clark 

National Forest), which presented many problems in 

the development of major mining industries within 

the multiple-use program of the U.S. Forest Service. 

Since 1970 the Viburnum Trend or New Lead Belt 

has ranked first in the world in lead ore production. 

[3-5] Zinc has also increased so that Missouri ranks 

second in the nation, passing both Tennessee and 

Colorado, and is challenging New York for first 

place. Missouri also ranks fifth and seventh, respectively, in the United States for the production of silver and copper. 

The hilly topography of the area confines discharges from the mining and smeltering operations 

in separate stream systems; hence pollution effects 

can be determined for individual mines, mills, and 

lead smelters. Streams that flow into the area from 

the eastern edge of the drainage basin (Black River 

watershed) are not affected by either the mining 

development or populated regions and so can be 

used as controls. |6| The forested Ozarkian terrain 

135 

I 

r 
• I ST. LOWS 

T34N 

T53N 

FIGURE 7-1.—Location of ftw Viburnum Trand in th» MM * LMd Belt of southeast Mhsouri. 

has a decided effect on wind direction, which affects 

the movement of stack emissions and other possible 

industrial and domestic sources of air pollution. 

While the prevailing wind direction is from the west 

and south, the rolling terrain makes it difficult to 

determine air pollution effects on the forested or 

cleared areas near the mining and smelting operations. 

Galena (PbS) is the principal ore mined, with lesser quantities of sphalerite (ZnS), pyrite (CuFeS), and 

silver recovered as economic coproducts. Geologically, the lead is disseminated throughout the 

Cambrian-age Bonneterre formation, mostly a dolomite at depths ranging from 700 to 1,200 ft. Since 

the producing formation also serves as a major aquifer, most mines must employ constant pumping 

(ranging from 3,000 to 6,000 gal/min.) to prevent 

flooding. This inflow of water has reduced mine dust 

as a potential problem, but the mine water pumped 

to the surface contains appreciable amounts of fine 

galena and associated trace metals as well as spillage 

from underground repair and equipment maintenance operations. 

Generally, the ore is crushed underground and 

hoisted to the surface in skip loaders. Water is 

pumped from the mines to the surface, and part of it 

is used in the milling procedures. Chemical reagents 

may be added to separate lead, zinc, or copper minerals from the finely ground rock by flotation. The 

remaining mine water is treated in large sedimentation or tailings ponds. 

The lead and zinc (and sometimes copper) minerals from the flotation process are pumped into thickeners where the concentrate settles. The water, excess flotation reagents, and colloidal and supercolloiI 

dal minerals are then discharged as a milling cftta* 

The concentrate Is vacuum dried and transported to 

smelters for final conversion to metal. A I\T*« 

mine-mill production flow chart is illustrated in r» 

ure 7-2. 

The water and tailings waste from the nuntng mi 

nulling operations are discharged into settlement md 

treatment lagoons, generally known as Ushnji 

ponds. Dams for the ponds are usually comtruiid 

from tailings (generally 200 mesh m size), which rt 

centrifuged into fine and coarse fractions durinj du 

ore concentration process. After the dams art ct» 

structed, the taiHngs and other liquid wastes at » 

traduced upstream until the lagoon is effecrnvh 

filled. The lagoons serve as settling basins for i-t 

residual tailings to biologically degrade any <pr« 

organic reagents discharged from the milling pnx 

ess. Figure 7-3 is a production flow chart drpkr^ 

a typical modern smelting operation with vmo» 

types of emission controls. 

Pollution Sources 

Figure 7-4 summarizes 

potential'sources for er* 

ronmental contamination by heavy metals sssoriaa* 

with (he development of a major lead mining repos 

The most obvious source of lead emissions h *» 

smelter owned by the AMAX Lead Co. H»_3B» 

main stack discharges a baghouse effluent minimi 

28.5 Ib/h of total particulates under normal opens 

mg conditions; 5.1 Ib/h is particulate lead. Lea * 

vious sources of lead near the smelter are rt« *> 

called fugitive sources such as truck " J TM*? J 

transport of ore concentrates and windblown esj 

from metal concentrate piles (containing up <° " 

Wat M-T»picil mlr«wnlll production how chart. (Courtw of AMAX LMd Co.) 

nftay induction "° * churl. __ _ 

-138 

is, : 

mu ti ts'£ m 

JaaajmwnUodCo. ot Mhamrt 

< * M.-Smafler-reflnary production flow chart. (Courtesy of AMAX LMd Co.) 

_1S7_. 

'v t 
LEW COM:, ar 

ROAD OR RAIL 

TO SMELTER 

OR STORAGE 

TRANSPORT 

In ROAD OR RAIL 

TO OTtCR 

SHELTERS ANO 

OTHER ECOSYSTEMS 

FINISHED 

METAL 

PRODUCTS 

FIGURE 7-4.—Source, of ttsca metals In tha environment of 

the New Lead Bert ot southeastern Missouri 

percent lead by weight). By comparing particle size 

distributions. Purushothaman IT) has theorized that 

these are the ftialor sources of lead deposited within 

about 3 mi of the smelter. At greater distances, the 

stack emissions are the prime contributors of lead to 

the soil. 

Other sources of lead and trace metals released to 

the environment include: [81 

(1) Mine water. Most mines must remove from 

the operational levels water that is generally 

rich in dissolved CO2, carbonates, minor hydraulic and oil pills, unused blasting materials, 

and finely ground rock. Some formations (not 

in the New Lead Belt) may have pyrites in the 

ore; depending on the amount present, they 

may produce acid conditions and concomitant 

high levels of dissolved metals. 

(2) Mill waters. These waters include finely 

ground gangue (rock containing no ore), unrecovered minerals, excess organic milling reagents, and dissolved and suspended heavy' 

metals. 

<3) Tailings. This gangue material represents the 

largest volume of solid wastes and is used to 

construct the tailings dams; it contains widely 

varying amounts of lead, zinc, etc. The tailings 

are finely ground (less than 200 mesh) and may 

blow onto the soil or wash into streams. 

(4) Concentrates. These materials, containing approximately 70 percent lead by weight, not 

only blow onto soil and plants, but may also 

be washed away to the soil and streams. 

138 

Transport in open vehicles and railroad cars 

aids in disseminating these materials. 

(5) Smelter emissions. In addition to the stack and 

fugitive emissions from blowing concentrates 

and dusts from the sintering operations, bquxj 

wastes from lagoons and acid neutralization 

systems may inadvertently contain heavy rottals. In the New Lead Belt, the smelter operations are unusual in that both Hquid and air. 

borne wastes frequently contain anornaloui 

amounts of cadmium. This element, normally 

present in the ore in minute quantities, it an. 

parently concentrated during the smeltTM 

process. 

This rapid and continuing industrial development 

in a rural forest ecosystem has presented a unique 

opportunity to studying tthe transport and distribution of lead and associated trace metals from minus 

milling, and smelting operations. [9-10] Research 

into the various ecosystem compartments as related 

to lead in air, soil, vegetation, and water haa determined background values, established natural Duelines, and evaluated the lead mining and smellinj 

industries as sources of trace metals in the environment. Ill] 

LEAD IN THE AIR 

The distribution of heavy-metal bearing particles 

emitted into the atrnosphere from lead mining and 

smelting operations forms a basis for estimating Ihe 

transport of heavy metals to other components of 

the total ecosystem. Investigations of the atmospheric transport and distribution of lead in the New Lea) 

Belt Involved three specific objectives: (1) to determine the strengths of the stationary and mobdt 

emission sources of particulate lead and other heavy 

metals in the smelter area; (2) to characterize dc 

particulate lead emissions from the stack, particulate 

lead in the air, and windblown particulate lead; and 

(3) to determine the short-range distribution of particulate heavy metals in air and on the ground. 

Source Strength and Characterization 

The sources of particulate lead and other heavy 

metals in the AMAX smelter area fall into two categories. First, the process-oriented stationary 

sources—in this case, the 200 ft main stack rectivrra) 

effluent gases from a baghouse attached to the Hast 

furnace. In addition to the blast furnace off-gases, 

the baghouse received the weak off-gases from the 

sinter machine. The second category is the industrial 

sources (mobile) such as trucking and railroad operations, exposed piles of process materials, dust on 

the ground, and spillage around the smelter. 

A sampling study to determine particulate loadirej 

and size distribution in the stack gas involved three 

tests run under normal smelter operations. The Results are shown in table 7-1 in terms of particulate 

loading and emission rates. The average mass errdV 

sion rate of heavy-metal bearing particulates «*• 

28.45 Ib/h; particulate lead amounted to 4.66 Ib/h or 

1173 

1/71 

11/13 

Aewae 

TABLE 7-1.-

Psrticulates 

Ct/DSCF" 

0.0122 

0.0240 

0.0111 

0.0158 

Ib/h 

20.87 

38.69 

25.80 

28.43 

'tack particulate emltttont pom AM A X lead metier under normal operating conditions 

Lesd 

Gr/DSCF 

0.0029 

0 0026 

0.O02I 

0.002S 

IWti 

4.9S 

4.18 

4.85 

4.66 

Zinc 

&/DSCF 

0.00027 

0.00016 

0.00021 

0.00021 

Emission rate* 

Ib/h 

0.47 

0.339 

0.495 

0.435 

Copper 

Cr/DSCF 

B.IX10-1 

8.3x10" 

3.2x10-* 

7.2X10-" 

Ib/h 

0.0140 

0.0134 

0.0120 

0.0131 

Cadmium 

Ct/DSCF Ib/h 

0.00011 0.193 

0.00010 0.157 

0.00012 0.281 

0.00011 0.210 

Pro****: •infer mac hint and bi n I furnace op«f attorn. 

Tot point I 3 btctiotue outkt flue. Btphouae recctvod ilnter machine and Witt furnace off-fw n only. Tht ibitar machine «ron» cases a n 

j f f In an actd plant fot SO, recovery. 

^Grains per drjr itindard ft V 

tf percent by weight of particulates. At tbe same 

oe, particulate zinc, copper, and cadmium were 

bcharged at rates of 0.435, 0.013 and 0.21 Ib/h, 

npectWely. Although the ambient levels and deportion rates of settleable particulate cadmium were 

aatantiy lower than those of particulate copper, 

tc emission rate was almost 20 times higher than 

til of copper. There are two reasons for the high 

mission rate of particulate cadmium. First, lead ore 

ntcentrate from the New Lead Belt contains a very 

Mgfa concentration (930 Mg/g) of cadmium; [12] in 

nst concentrates the Zn to Cd ratio una around 

JO, but the New Lead Belt ratio is closer to 100. 

xxondly, copper was found to be associated with 

articles of 7 jim mass median diameter 

MMD). Such particles are more efficiently removed 

othe baghouse than cadmium, which was attached 

Bparticles of 1 pm MMD. The relative amounts of 

copper, and cadmium in the stack arassions 

• n approximately 1(10, 1/400, and 1/20 of lead, 

Rspectively. 

The particulate emissions from the stack were 

tenderized with an Anderson in-stack cascade 

qactor. (table 7-2) Approximtely 25 percent of the 

articulate lead, zinc, and cadmium was associated 

•ilh 0.74 urn particles; in the case ot particulate 

opper, however, about one-half of the amount was 

concentrated in particles greater than 8 jim. This 

•Bests that a greater percentage of the particulate 

copper would be removed by the baghouse, while 

am of the particulate cadmium would escape 

(rough the stack. 

The size distribution of the heavy metal-bearing 

particulates is shown in figure 7-5. Approximately 90 

percent of the particulate lead, zinc, and cadmium 

was less than 10 to 20 Mm, with a MMD of I to 1.5 

ion. However, the (particulate copper had a MMD of 

7pm, with 25 percent larger than 12Mm. 

Generally, particles with an equivalent size of 10 

to 20 jim, depending upon their density, are considered to have such small settling velocities that they 

tend to remain suspended fat the atmosphere for long 

periods ot time and hence are subject to long-range 

rather than short-range transport and dispersion. 

Assurning the average density ot lead-bearing particles to be 10 g/crrp. then settling velocity would be 

affected by the particle diameter under a given set of 

conditions. In short-range transport of lead. It can 

be assumed that gravitational sedimentation win be 

negligible for particles with settling velocities « I 

cm/sec. (13) Hage's data (141 on the settling velocity 

of smooth spherical particles with a density of 5 g/ 

cm' are given by Vander Hoven [13] as a function 

of particle diameter and altitude, forticic size was 

reported to be the dominant factor affecting its velocity. Accordingly, particles with diameters of less 

than 10 Mm are not affected significantly by gravitational settling. 

Windblown dust in the smelter area was character 

ized wilh an Anderson nonviable sampler and aluminum foil collection plates at a location exposed to 

trucking activities. Tin sampling was carried out for 

4.5 h at I ft'/min. The results are summarized in table 7-3. 

TABLE 7.2.-ftrttrle ffsStro/fteerv inennlDeart^fAsrrgculrrf 

emttraMU from a primary lead tmetter ttack 

>* 

o 

1 

1 

4 ) 

1 

< 1 

•dap 

tot 

ECD' 

Otfnl 

12.7 

8.0 

3.3 

3.75 

2.33 

1.2 

0.74 

0.49 

Lead' 

S40 

305 

365 

2SS 

335 

720 

1,2 35 

665 

380 

Amount collected (of) 

Zinc 

33 

39 

27 

26 

30 

64 

108 

72 

71 

Cadmhun 

14 

15 

12 

9 

II 

21 

47 

33 

26 

Cooper 

4.5 

4.3 

3.7 

3 

0.7 

1 

1.2 

1 

0 

Lead' 

10.8 

10.1 

7.3 

3.3 

6.6 

14.4 

24.6 

13.3 

7.6 

Percent of total mass 

Zinc 

7.4 

1.3 

5.7 

5.5 

6.4 

I3.S 

219 

15.3 

15 

Cadmhun 

7.4 

8 

6.4 

4.9 

5.9 

11.2 

25 

17.6 

13.6 

Copper 

23 

23 

18.9 

15.3 

3.6 

S.I 

6 

5.1 

0 

'Corrected affective cutoff dtemeter et SO percent Impaction efficiency. 

'>'f.|l4| . 

13S 
% Greater Than 

BO 70 60 50 40 30 20 

20 » 40 SO CO TO DO 90 99 969 9 

Cumulative Weight % Lett Than Stated Site 

flQUR E 74.—S) » dlstiltMiUon o^ 

More than 90 percent of the windblown particulate 

lead was associated with particles greater than 3.3 

/im, while almost equal amounts of particulate copper were concentrated in each particle cut-off size 

ranging from 0.43 to II nm. The particulate lead 

concentration decreased from 40.3 to 0.8 ^g/m'; particulate copper levels had two peaks of 3.8 Mg/m'. 

Apparently, the dusts generated by the trucking activities, as well as that resuspended by the wind, are 

significant contributors to the high levels of lead and 

other heavy metals observed in the surrounding 

area. 

The particle size distribution of lead and copper In 

the fugitive emissions is presented in figure 7-6. 

Only two-thirds of the particulate lead (with a MMD 

of 9 .urn) were less than 11 um in diameter; however, 

approximately 83 percent of the particulate copper 

(MMD = 3.5 um) could be attributed to particles of 

11 Mm diameter or less. 

Transport and Distribution of Settleable 

Particulate Heavy Metals 

The transport and distribution of settleable putt* 

culate lead and other heavy metals were determined 

by field measurements with,twenty dustfall stations 

in an area 3 mi by 3 mi surrounding the smelter, (fig. 

7-7) As expected, the deposition rate for settleabk 

particulate lead decreased with distance in each 

direction from the stack. The total deposition rate in 

any direction was a function of the pevailing wind. 

The transport of settleable particulate zinc, copper, and cadmium followed the same trend as the 

particulate lead except that the deposition rates of 

Zn, Cu, and Cd were approximately 10, 20, and 100 

times, respectively, lower than that of lead. Tha 

gives 8 cadmium-to-copper ratio of about 0.20. This 

compares with the cadmium-to-copper ratio in stack 

emissions of about 20; thus the cadmhim-to-copper 

ratio in the settleable particulates is several orders 

TABLE 7-1,-ChtTittertxertonofwtmJbloHtt fftigtttPt) particulate 

heavy metab tn the vicinity of a primary lead tmetter' 

Stage 

0 

Backup 

nitei 

Oim) 

11 

7 

4.7 

3.3 

2.1 

0.65 

0.43 

Amount collected (jig) 

Lead 

308 

268 

148 

128 

46 

6 

0 

0 

IS 

Copper 

29 

29 

29 

24 

24 

29 

29 

19 

6 

Percent of total matt 

Lead 

33.3 

29.2 

16 1 

13.9 

3 

0.7 

0 

0 

1.6 

Copper 

13.3 

13.3 

13.3 

II 

11 

13.3 

13.3 

8.7 

18 

Concentration Oaj/n'l 

Lead 

40.3 

35 

19.5 

16.7 

6 

0.8 

0 

0 

1.9 

Copcet 

3.1 

3.1 

3.1 

3.1 

3.1 

3.1 

3.1 

' Zinc end cadmium value* were I m end hence ere not repotted. 

'Corrected effective evil off diametcf at SO percent Impactlnn tfYlctencr. 

140 

ZO 90 40 90 60 TO 

Cwrxjlotrve Weight % Let* Than Stated Size 

GURE 7-6—Si » distribution o f wlndbtown particulate lead 

4 copper around a primary lead smelter. 

I inignftude lower, suggesting that fugitive sources 

»the major contributors rather than stack enrisua. 

j The directional distribution of settleable perticutft zinc, copper, and cadmium indicated again that 

'smiling winds were responsible for higher deposipt rates at the south, east, and northwest stations 

as compared with the west stations. The proximity 

of the Magmont Mine tailings pond did not increase 

the deposition rates at the 1 and 1.25 mi stations. 

The settleable particulate lead, zinc, copper, and 

cadmium reached background values of about 55, 9, 

3, and 0.3 mg/m2-mo, respectively, at a distance of 

1.5 mi from the smelter. 

The radial distribution of settleable particulate 

lead around the AMAX Smelter is shown as isopleths in figure 7-8. The isopleths were obtained by 

using the geometric mean values of the deposition 

rate at each station. (13) 

In summary, transportation activities Inherent to 

the smelting industry, combined with meteorological 

conditions that cause intermittent and unpredictable 

amounts of fugitive dusts are major factors in the 

accumulation of heavy metal particulates within tbe 

smelter area. Beyond the smelter boundary, the 

loading of settleable particulates drops to low yet 

significant values. 

Transport of Ambient, Suspended, Particulate, 

Heavy Metals 

The transport of ambient, particulate lead, and 

-other heavy metals, may best be considered as both 

short* and long-range. Short-range transport is due 

to the rapid settling of larger particulates, while 

smaller particles remain suspended in the atmosphere and are transported over longer distances. 

F*A E 7-7.—Location ol d r monitoring stations around a 

potty lead smelter. 

FIGURE 7-8—Aadlaf distribution of settleable parttcutat* lead 

around a primary lead smelter. 

- M1 „ 

- "0 

1

 tn 
36 

34 

32 

30 

28 

26 

24 

22 

T=20 

0 

* I 8 

I,. 

g S '« 

u 3 « 

10 

s 

s 

4 

2 

n 

wrWomtrn 

Geo. Mean 

klifsBrTBun. 

. 

• 

' 

t») 

( ) Ma of Biweekly Sample* 

<29J 

i 

g» p a es 

Oistonca from Stack, thousands fast 

RGURE 7-9.—Short rang* transport of ambient lead. 

The short-range transport of the ambient lead was 

monitored with five high-volume stations within 

6,000 ft of the smelter stack as shown in figure 7-9. 

Bi-weekly samples were collected with 8 in. by 19 

in., Type A, glass fiber filters from June 1972 to 

June 1974. High-volume cascade sampling was also 

done to evaluate the characteristics of the particulate lead and other heavy metals. 

The concentration of ambient particulate zinc was 

often equal to or less than the blank value of the 

glass fiber filter, in spite of the fact that samples 

were taken for a 24 h period. [13] This was corrected by using Whatman 41 cellulose, filters with a low 

zinc content. 

The short-range transport of ambient suspended 

particulate lead indicated that the lead level deTABLE "i-A.-Short-range transport of ambient impended 

particulate copper ond cadmium around a 

primary lead tmetter 

Distance 

from 

etack (ft) Geo Mew 

Concentration Oig/m*) 

Copper 

Max Min Geo Mean Max Mm 

1,140 0.25 2.3 0.02 

3.875 0.07 0.75 0.01 

4,250 0.03 0.5 0.01 

5.250 0.03 0.18 0.01 

5,750 0.05 0.4 0.01 

142 

0.11 6.68 0.01 

0.02 0.34 0.01 

0.03 1.68 3.01 

0.02 2.29 0.01 

0.04 0.7 0.01 

% Greater Than 

19 tS 9S 90 60 TO 60 SO 40 30 

20 SO 40 90 80 70 

bmetothrt Weight % Le« Than Stated Six* 

FIGURE,7-10.—Size distribution of ambient particulate heavy 

metals near a primary lead smelter. 630 ft SSE of stack. 

creased with distance, ranging from 6.4 Mg/rrP tt 

1,140 feet to I Mg/m3 at I m. from the smelter stack. 

However, the maximum levels varied from 31.5 to 

13.8 Mg/m3 depending upon wind speed and direction. 

The short-range transport of ambient suspended 

particulate cadmium and copper is shown in table 7-

4. The lead-to-copper ratio was about 25 at the nearest location from the stack and about 30 at the farthest point. The lead-to-cadmium ratio was about 60 

closer to the stack and about 40 at the more distant 

location. 

The physical characterization of ambient partjeolate lead and other heavy metals was achieved with 

a high-volume particle sizing head and a 12 in. diameter glass fiber collection disc at 20 ft'/min. Samples 

were collected for 48 to 72 h to obtain sufficient 

amounts of heavy metals for analysis. Figures 7-10 

and 7-11 show the size distribution of ambient heavy 

metal-bearing particulates at 630 and 1,425 feet SSE 

and ENE, respectively, of the AMAX smelter stack. 

The MMD of the lead-bearing aerosols varied from 7 

to 11 Mm, and that of particulate copper ranged belt Greater Than 

_»t«f (s to eoro«o9040 90 » to s » i 

I ' I 

I 

At 1423 ft. CMC of 

-i— i to &"fe 4oso«b ft to fth rt tV* 

Cumulative Weight % Lett Than Stated Site 

Figure 7-11.—Size distribution of ambient partlcutate has** 

metals near a primary lead smelter, 1.42S ft ENE of stack. 

4 3 

Jet Plata No. 

FGURE 7-12.—Relative concentration ot ambient pertieulate 

Sevy metals as a function of particle size. 630 tt SSE of 

r 

men 1.6 and 2.5 ,um. These sizes correlate with 

base for windblown dust shown in figure 7-6, conjtrming that the heavy metals are of windblown orim. In the case of ambient zinc and cadmium, about 

|B to 65 percent of the aerosols were larger than 7 

m, with a MMD of 2 to 4 Mm. 

The size class distribution of heavy metals was 

watoated in terms of relative concentration as a 

function of particle size, (figs, 7-12 and 7-13) This 

Tpe of representation brings out some interesting 

points that are not evident from the particle size distribution curves shown in figures 7-9 and 7-10. The 

wbient lead, zinc, and cadmium were concentrated 

o7jun and less than 1.1 Mm particles; however, the 

mbient copper was mostly associated with particles 

ess than 1.1 Mm in diameter. 

Jet Mot* No. 

nouflE 7-13.—fte*attv» concentration of ambient particulate 

heavy metals as a function of petitae size, 1.425 ft ENE of 

stack. 

The ambient concentrations of heavy-metal particulates determined with the high-volume impactor 

closer to the smelter stack are presented in table 7-5. 

The concentration of heavy settleable particulates 

and the decrease in heavy metal concentration with 

increasing distance could be attributed to the change 

in the wind direction over a period of 48 h. 

CONCLUSIONS 

Based on data presented and discussed above, 

several conclusions can be drawn concerning the 

distribution of settleable particulates and suspended 

particles of lead and other heavy metals due to emissions from lead mining and smelting operations in 

the New Lead Belt area. It should be emphasized 

that the lead industry has utilized these data to 

change or improve the various operations and COOTABLE l-S.-AmMent particulatt heavy metalleweh as obtained by htgh-vobme tmpactae 

From Mack Concenuatton (wg/m*) 

Stmpthtg 

period 

DiManre 

(ft> 

Doectton Zinc Copper Cadmium 

tar 12-15.1973 

My 9-11,1973 

630 

1.425 

SSE 

ENE 

18.68 

8.63 

1.74 

0.64 

1.1 

0.B6 

Oil 

0.08 

143 
trol many of the problems noted in the research 

findings. The conclusions are: 

(1) During the period of study, the major sources 

of lead and other heavy metals within I mi of 

the AMAX smelter were the fugitive dusts: 

these caused the deposition of settleable particulate lead in excess of 2 g/m2-mo in the 

smelter area. Numerous changes have been 

made to alleviate these conditions. 

(2) The particulate emissions from the smelter 

stack were of significance in the long-range 

(greater than 1 mi) heavy-metal deposition. 

(3) The short-range ambient suspended particulate 

lead and cadmium concentrations reached levels of 32 and 6.7 *g/mJ in ENE and NNW 

directions, respectively. 

LEAD IN SOIL 

Soil and geochcmica! studies were carried out to 

(I) determine the extent and. characteristics of soil 

pollution patterns produced by the various smelting 

and mining activities, (2) determine the chemical 

and mineralogfcal characteristics of the pollutants 

emitted from various sources, (3)_assess the relative importance of the individual pollution sources, 

and (4) determine the geochemical behavior and 

mobility of polluting heavy metals. 

The seven active lead mines and their associated 

mills in The New Lead Belt are potential pollution 

sources through windblown material from stored ore 

concentrates and, to a lesser extent, tailings. One 

lead smelter of the AMAX Lead Co. of Missouri is 

located in the district, with a second smelter, ASARCO. about 28 mi lo Ihe southeast. Both smelters 

started operation in 1968. 

Sampling and Analysis 

Most of the study area is heavily forested with 

oak and local stands of pine. Since early data [16] 

indicated that heavy metals accumulate in the 

decaying leaf litter with only minor amounts reaching the underlying mineral soil, emphasis was placed 

on the collection and analysis of the organic hori-

; zons. The samples of leaf litter from soil profiles 

were described according to a proposed international 

system for the description of soil horizons. 117] The 

following abbreviations are used for the various 

samples: 

W. Oak = leaves taken directly from white oak 

trees 

Of - partly decomposed leaf litter 

Oh = well-decomposed leaf litter, usually more 

than I year old 

O = undistinguishable leaf litter 

Soil samples were classified according to their depth. 

Crass samples were collected from scattered pastures in the vicinity of the smelters. These samples 

were subdivided into "standing grass" and "malted 

grass." The vegetation was dried at 100°C and then 

ground in a Wiley min. The soil samples were also 

144 

dried at 10CPC and passed through an 80 mrth 

(0.171 m) sieve to remove pebbles. Most of ihe 

samples were analyzed for read, zinc, copper, and 

cadmium by atomic absorption spectroscopy. 

Considerable variation was found in the hravymetal concentrations of replicate samples from hea£ 

ily contaminated areas, (table 7-6) This was due to tht 

nature of the leaf materials rather than the analytical 

techniques, and it emphasizes the need for a rela. 

tively large number of samples. It is quite likely thai 

the heavy-metal particulates are not uniformly div 

tributed within the litter layers. It is also difficult lo 

sample specific organic horizons without some miiing from adjacent layers. In addition, heavy-metal 

particles may be partially removed or concentrated 

in certain parts of samples during collection and 

preparation for analysis. These same factors were 

also evident in grass samples. 

Background Concentrations 

Soil samples from 125 stations covering most cf 

the New Lead Belt do not indicate the natural occur. 

rence of abnormal heavy-metal concentrations in the 

soils of the district. High concentrations can always 

TABLE 7-6.- Variation bl heery mead content ofduptkate led 

Utter 10flayer) and toa templet (0-1 pt depth)' 

Zn 

Average 70,000 

Range 34.00O45.0O0 

Standard 

derialkin 16/423 

Ot-lesr titter Cig/g) 

1.460 

1.400 

1,800 

1.530 

1.240 

1.280 

1.400 

1,360 

1.434 

1.240-1.800 

174.4 

1.400 

1.210 

1.500 

1.120 

920 

I.I 10 

I .MO 

1.220 

1,201 

920-1400 

Sog. 0 to I tn. depth (jig/g) 

3.200 

1.260 

2.160 

1.020 

1.210 

580 

1540 

1.860 

Average 1.663 

Range 580-3.200 

Standard 

deviation 812.4 

200 

125 

160 

130 

100 

130 

150 

145 

143 

100-200 

45 

2080 

t. Sample oolfected erjthbi I m1 located 0.25 nti northeast 

or tmelter. 

40-70 

8O-I00 

35-50 

50-100 

15-20 

35-50 

50-70 

12-17 

25-60 

10-20 

6-8 

8-11 

3-6 

5-7 

1.5-4 

0.7-1 

0.9-1 J 

< 0 J 

<0J-I.6 

<0J 

TABLE 1-1.-Estimated background concentrattont of 

heery metals 25 to SO ml from AMAX smelter 

purler Of 

data Oh 

«aUngrre«s 

intdptn 

4lstinai 80 e 

i related to potential pollution sources. The backorjttd concentrations reported in table 7-7 are 

std on samples collected at a distance of 25 to 30 

i from the AMAX smelter. 

nd Distribution In Soil Profiles 

Analysis of soil profiles from oak forests in the 

entity of the smelters, which have been operating 

tm 4 to 7 years, indicates that most of the lead 

rJ other heavy metals are still in the leaf litr. Only Ihe lop I in. of the underlying mineral soils 

lows elevated levels in areas of heavy contaminant. The concentrations of lead usually approach 

i reach background at depths of 2 to 3 in. (tables 

• and 7-9) Thus jf data from soil samples below 

t leaf litter were used alone, both the intensity and 

TABLE l'O.-Heary metals tn tot! profiles 

0.2 ml from AMAX smelter 

1(0.25 ht„ pine needles, 

us leaf litter) 

110.23 in., sol) * oak 

W litter) 

4.Z3 bl. sou 

M l in. soO 

M n. soil 

lie. log 

lie. toil 

<b.<oll 

Zn 

W l > 

39.000 

3.200 

840 

330 

20 

<20 

<20 

1.850 

1.330 

ISO 

80 

60 

50 

50 

50 

2.200 

760 

100 

35 

20 

<I0 

<I0 

<10 

It extent of the pollution patterns would be seriosiy underestimated. In contrast, elevated levels 

ere found to a depth of several inches in soil samrs taken from profiles without a cover of leaf fitMtabte7-I0)[l8] 

Wributlon Patterns of Lead Near Smelters 

Since the distribution patterns of lead around the 

n smelters differ in several respects, the results are 

fscussed separately. 

TABLE 1-9.-Heary metals tn tod profiles 

0J ml from AM A X smelter 

In 

(nVg) 

•fuller (0.5 In.) 

«Jin. .ol] 

184.5 in. soO 

il.Ota. mil 

> la. soil 

7400 

380 

<20 

<20 

330 

100 

50 

30 

150 

30 

10 

<I0 

<I0 

AMAX Smelter: Soil samples were collected along 

six sampling lines radiating for a distance of 25 to 30 

mi from the smelter. These lines generally followed 

highways, but the samples were collected at least 

1,000 ft from paved and well-traveled roads. The 

area showing elevated lead concentrations in the leaf 

litter is slightly elongated to the north and south 

from the smelter, which agrees with the prevailing 

wind directions. At a distance of about 1/4. mi from 

the smelter the lead concentration in the Oh layer is 

between 30,000 and 60,000 egfg, with some samples 

as high as 130,000 ug/g. At a distance of 0.5 mi, the 

lead concentration is in the range of 20,000 to 45.000 

Mg/g and then drops sharply for about 5 mi. Figure 

7-14 shows the distribution of lead, after 5 to 6 yearg 

of smelter operation, for a distance of 30 mi. The 

oldest well-decomposed leaf litter (Oh) contains Ihe 

highest lead concentrations. However, either the) 

recent leaf litter (00 or leaves collected from tree* 

would be suitable to establish the extent of the pollution pattern, especially if reaves are collected just 

prior to annual defoliation, thus allowing 'maximum 

time for derjosilion. 

It is interesting in this context to compare the distribution patterns of zinc, copper, and cadmium with 

lead. Cadmium and copper reach background concentrations at 15 and 10 mi. respectively, from the 

TABLE 7-10. -Heary metals In toll profits wtthoufeom 

of leaf litter located 0.23 mlfrom AMAX tmelter 

Pb Zn Ol 

toa/l) 

00.25 rn. soU 

0.25-0.5 in. toO 

0.51 in. soil 

l-2oi. soil 

2-3 tn. ion 

3-4 In. soil 

4.300 

SOO 

330 

100 

140 

160 

600 

70 

30 

50 

50 

SO 

140 

10 

10 

<I0 

<I0 

<I0 

smelter, while zinc rarely shows elevated values in 

leaf litter beyond 5 rrd from the source. Thus neither copper, cadmium, nor especially rinc could be 

used as indicators of lead pollution patterns. The 

differences in extent and intensity of the distribution patterns of the four heavy metals are only partially due to their relative cencentrations in the 

source (stack emission). For instance, zinc is emitted from the smelter in higher concenrratrons than 

either cadmium or copper. It appears that the solubilities of Ihe heavy-metal particles and their subsequent geochemical mobilities are of greater importance. 

Figure 7-15 shows the distribution of lead in pasture grass north of the smelter. Background concentrations seem to be reached at a distance of about 10 

mi. As expected. Ihe highest lead concentrations are 

in the matted grass rather tn in the standing grass. 

ASARCO Srnettfr: The distribution pattern of lead 

in leaf litter around this smelter is strongly elongated 

to the north and south. Background concentrations 

to the north and south are reached at 8 to 10 mi 

from the smelter and at about 5 mi to the east and 

west. The pronounced elongation of the polluted area 

_ 14S 
%i 

r. 

I 

TOOO 

3000 

2000 

woo 

TOO 

500 

400 

am 

• 

TO 

90 

90 

ZO 

10 

• 

:o 

.°o 

z 

. 

-

-

• 

9 

o • 

o 

• 

o "Of {purity ^oc/WfUMOOi 

• • Ooh (mm Iran trots(alt Jim) 

• •• 

°°o. 

8

B

 • • 

• 0 • • 

•° "e, So 

. . . 0 O 0 

• 

• • 

• 

•• • • » 

an as 

UeeMe tio» Siaae (eawel 

RGURE 7-t 4—Lead In Oak Leal Litter NNW ot AMAX Smelter. 

TOO 

9000 

9000 

2000 

1000 

TOO 

SCO 

300 

lao o 

f 

E TO 

SO 

30 

O 

• 

- O 

-

" 

-i 

9> 

• 

• 

1

 • • 

0 

• 0 

0 0 

••• 

* ' • • • 

• •StantflnQ Grow 

Q»Matt t Gran 

O 

• • 

0 

• • 

1111111111 1 

0 

• 

11 

0 

• 

0 

• 

i 1 1 

Dittanct tram Smart* (man) 

FIGURE 7-15—Lead in Grass Samples Collected North of 

AMAX Smelter In April 1S74. 

is probably caused by the location of the smelter m 

a deep north-south trending valley, as well as by the 

prevailing wind directions. In comparison, the distribution pattern for cadmium is similar in extent to 

lead, while those of copper and especially zinc tn 

much less extensive. 

The distribution of lead to the north of the smelter 

is shown in figure 7-16. Contrary to the distribution 

of lead around the AMAX smelter, the concentrations of lead near the ASARCO smelter is generally 

higher in the more recent, partly decomposed leaf litter (Of layer) than in the older Oh horizon. 

Pollution by Mining and Transport Activities 

Pollution of leaf litter by mining activities (essetv 

tially handling of ore concentrate and storage of tailings) does not appear to be as serious as that from 

smelter emissions. Samples taken along three sampling lines for a distance of about 4 mi from a mine 

indicate that some leaf litter samples within I mile 

may contain lead concentrations of several hundred 

thousand micrograms/gram. At greater distances, as 

well as in many samples close to the mine, the concentrations are at background levels. 

Transport of ore concentrate in open trucks and 

railroad cars does contribute high lead concentrations to the environment for a distance of up to 500 

ft. Data for leaf litter near a highway are shown in 

figure 7-17. Major pollution (in excess of 500 Mg/g) is 

generally restricted to a distance of 200 ft from the 

transport routes. Railroad transport appears to be 1 

less significant source than highway trucking. This 

aspect of lead pollution is discussed in more detail 

elsewhere in the chapter. 

Nature and Mobility of Metal Pollutants Near 

Smelters 

Lead smelters have two potential poflution 

sources: emission through the stacks and fugitive 

sources, such as stored ore concentrate and dust 

blown from contaminated soil in the smelter am. 

Identification of the relative contributions from these 

sources is of major interest since the ultimate 

objective of pollution research is to help reduce or 

eliminate the causes. For instance, reducing stack 

emission at great expense would obviously not fulfill 

this goal, should the major source be fugitive dusts. 

The problem of source identification appears rather 

simple and straightforward since the two sources 

consist of materials that differ to some extent in 

their chemical and mineralogical compositions. However, experience has shown that the problem is less 

easily solved than might be expected. 

Paniculate matter that leaves the stacks is 

difficult and expensive to collect. However, baghouse dust is probably similar in mineralogy and 

chemical composition, an assumption supported by 

the comparisons of small amounts of particulates collected from the two sources. 

Lead compounds in baghouse dust have been 

identified by X-ray diffraction as PbSO*. 

PbO-PbS04, and metallic lead. In addition, the dust 

U o d In LMf Utter 

O = 0f 

• o°8 

• o

 # o ° 

• • •«••• • 

-t - 1 -

2 3 4 3 6 T 

1 Dlslrjnos non Snwltajr lirseas) 

JGURE 7-t6.—Lead In Leaf Litter North ot ASARCO Smelter 

Moor 

3000 

2000 

000 

700 

500 

LtMd In LMf Utter 

• •Oh 

• •Ot 

MOH • •• 

100 

TO 

30 

30 

20 

K) 

'•» 

'300 500 1000 

1 Distance, from Rood (tost) 

*3URE 7-17.—Lead In Leaf Litter near Highway 72. an Oro 

j'mcHng Route East ot Reynolds. 

of the AMAX smelter contains approximately 30 

percent W»S as the predominant lead compound. Tire 

amount ot PbS in the baghouse dust of ASARCO is 

less than 5 percent. The chemical composition of 

baghouse dust is typically in the range of SO to 60 

percent lead. I to 13 percent zinc. 0.25 to 13 percent 

copper, and 0.5 to 6 percent cadmium. 

Fugitive sources are essentially lead-ore concentrates with PbS as the major mineral and a composition of about 70 to 75 percent read and 0.03 to I 

percent cadmium. Fugitive sources, therefore, consist 

predominantly of PbS with a very high Pb:Cd ratio 

(about 1.000:1). while the Fb:Cd ratio in smelter 

emission is much rower (about 20:1). Also, the baghouse dust, especially at the ASARCO smelter, contains very little FbS. It might be expected, therefore, 

that areas with a high PbS content and a high Pb.Cd 

ratio receive fallout from fugitive sources, while a 

low PbS and low Pb:Cd ratio would indicate stack 

emissions as the major source. Unfortunately, the 

available results are less than conclusive on this 

point. Concentrating lead compounds from soil or 

leaf litter for quantitive X-ray analysis is difficult. In 

addition, this method is not very suitable near the 

AMAX smelter because of the high FbS content of 

the baghouse dust. Use of the Pb:Cd ratio along a 

detailed sampling tine north of the AMAX smelter 

was of limited success. The Pb:Cd ratio ranges from 

175 to 275 for a distance of about 0.5 mi from the 

smelter. From 0.5 to 8 mi the ratio ranged from 100 

to 175: from 8 to 30 mi. the range was from 60 to 

100. Based on these results, a tentative conclusion 

147 
would be that fugitive sources are a significant contributor for a distance of at least 3,000 ft. This conclusion si supported by the occasional microscopic 

observation in soils of this area of material that appears to be slag. 

The reason that the Pb:Cd ratio does not dearly 

delineate the relative significance of the different 

sources becomes more obvious when the solubilities 

of the heavy metal compounds are considered. For 

example, solubility studies of baghouse dust (table 7-

11) indicate that cadmium is more soluble than the 

other three heavy metals, especially lead and copper. This could increase the Pb:Cd ratio in the leaf 

litter. Ongoing studies also demonstrate (table 7-12) 

that the natural water-soluble organic (humic) acids 

present in the decaying leaf litter significantly increase the solubility of lead, zinc, and copper compounds. In addition, the various lead compounds 

have different solubilities, PbS being only slightly 

soluble while PbSO4.PbOPbSO4.-and metallic Pb 

are much more soluble, (table ,7-12) Experiments 

with ion-sensitive electrodes indicate that lead and 

copper become strongly complexed and zinc weakly 

complexed by the organic acids. At a low pH (about 

4.5). cadmium remains primarily in the ionic state. 

In their complexed state, the heavy metals are less 

easily adsorbed on soils or precipitated, thus becoming both more mobile and easily removed. [19] The 

pathways of dissolved heavy metals are not yet fully 

understood. However, considerable amounts are 

removed by runoff during heavy rains, a point discussed elsewhere in this chapter. Analyses of runoff 

water after a period of dryness revealed up to 500 

fig/1 lead, 4,800 M&fl emc, flhd I94^g/1 cadmium after 

filtration through a 0.45 pm mill.pore filter. As the 

result of these different Solubilities and probable 

subsequent mobilities, the Pb:Cd ratio in the leaf litter changes, and tt$ is enriched compared with 

other lead compounds. 

In this context, the differences in pollution patterns of the AMAX and ASARCO smelters are of 

interest. The much lesser extent and intensity of pollution around the tatter is partially caused by such 

factors as lower production and differences in the 

treatment of ore concentrate and baghouse dust. 

However, differences in the mineralogy of the two 

stack sources may also have a major influence. 

Stack emissions at AMAX contain a high percentage 

TABLE 7-1 ..-Solubility of lead compound! tn water (HtO) 

and natural organic adds (OA)* 

TABLE 7-1 Z.y-Sotubaity of lead compounds m 

and natural organic acids (OA)' 

AMAX 

(main baghoase) 

ASARCO 

(blast furnace) 

ASARCO 

(sinter plant) 

OA 

H,0 

OA 

H,0 

OA 

H,0 

Pb 

16.6 

4.8 

30.0 

4.2 

17.6 

10J 

Zn Co Cd 

(percent sotnbfc) 

61.4 

13.6 

38.6 

3.1 

30.0 

18.1 

4.2 3S.8 

<3.3 33.8 

12.9 57.8 

<S.O 62.6 

2.8 71.8 

<l.n 68.8 

'Conditions: pH 3.B.SOm(dtm In 100 ml,40 n.OA -0.01 

ptrc*nt. 

148 

PbSO. 

PbO-PbSO, 

PbS 

Pb 

HtO 

'Conditions: 0.03 g nmpte, 100 n 

pH 5.5,34(1. 

I OA (0.01 pernor) or H.O, 

of rather insoluble PbS, thus permitting a buildup of 

lead a considerable distance (10. to 20 mi) from the 

smelter where the deposition rate is small. In contrast, emissions from ASARCO consist largely of 

the more soluble lead compounds, and 10 mi north 

of the smelter the rate of deposition may be exceeded by the rate of solution and subsequent removal of 

lead. If these conjectures are -correct, then the area 

around the smelter that receives heavy metal fallout 

Is actually larger than that currently showing elevated soil lead values. Also, changing operational procedures in smelters to eliminate emission of insoluble lead compounds such as PbS would perhaps result in less extensive and intensive soil pollution. Al 

the same time, release of more soluble lead compounds would probably result in higher heavy metal 

pollution of streams during periods of runoff. 

Effects of Metal Mobility on Leaf Utter and 

Biomass 

t he effects of the Increased mobility of heavy 

metals, as a function of humic acids Hi the leaf titter 

and soil, are being jointly investigated by the University of Missouri-Rolla and the Oak Ridge National Laboratory. (201 This work was being done on tht 

Crooked Creek watershed, located near the center 

of the Viburnum Trend in the New Lead Belt. Tha 

watershed also forms the basis for the development 

and verification of a unified model of tbe transport 

of elements by atmospheric and hydrologk processes. 121) 

The high solubility of cadmium with respect to 

lead is of particular concern since there are indications that Cd may be moving into the mineral soil 

horizons more rapidly than H>. Cadmium is more 

toxic to plants and microbial organisms than lead, 

and its ultimate effect may be a disruption of some 

norma) ecosystem functions. 

Watson (22J has characterized the fitter horizon 

at selected sites on Crooked Creek according to 

biomass, macronutrient status, and heavy niead 

concentrations. She found a significant decrease in 

the biomass of the O2 litter horizon with mcreasini 

distance from the smelter. Over the same mge of 

sites, the Oi layer remains relatively constant. Concentrations of Cd. Pb, Cu, and Zn follow expected 

logarithmic decreases in concentration with increasing distance from the smelter. 

The effect on the O2 horizon biomass appears to 

be due to a reduction in the rate of decornpcailioo 

ajtjcrobial and arthropod activity. These deconv 

sing organisms are completely missing within V4 

of the smelter. There has also been some alterain the turnover rates of macronutrients, some 

retained in the litter while other have leached 

tan the system. The cause of this has not been 

Wertnined, but the long-time consequence could be 

(depletion of essential nutrients, with a correspond-

•I decrease in forest productivity. 

SUMMARY 

I Data from an intensive sampling program indicate 

bt heavy pollution of soils occurs from lead-smelt-

't% activities and to a lesser extent from mining and 

tilling operations. This has occurred during the 5 to 

f years of an estimated 60 year period of operation 

• the New Lead Belt. 

I The organic horizons are the most heavily contamjnted parts of soil-profiles in the surrounding forest 

isosystem. Except where bare soil is exposed to falW from emissions, only the top 1 in. of the minerk soil shows elevated levels of lead and other heavy 

fetals. Thus analyses of soil samples alone, rather 

'tan leaf letter, would have resulted in a serious 

iderestimation of the problem. 

Humic acids present in the leaf litter and soil entance the solubility of heavy metals m tbe decendot order of Cd, Zn, Pb, and Cu. Lead compounds 

re also differentially soluble in these acids with 

\KSOt the most soluble and PbS the least. These 

fflerential solubilities influence both tbe extent and 

intensity of pollution patterns. 

A major effect on tnt biomass of tha Oj litter horror, occurs within Vi mi of the smeller stack and 

wears related to an absence of decomposing 

organisms 

within the immediately affected area. 

Turnover rates and patterns of macronutrients have 

to been observed. While the long-term effects of 

these changes are currently a matter of conjecture, 

Ihey could result in nutrient depletion and a decline 

n productivity of the forest. 

LEAD IN VEGETATION 

1 Plants are often excellent indicators of certain 

lavinmmental contaminants due to their rapid phyIttoxic response to sulfur dioxide, ozone, herbtlooes, etc. Their response to other contaminants, 

nch as toxic heavy metals, may not be readily visi-

|bfc. However, analyses of their leaves, roots* or 

other tissues may serve as indicators of their geoIthemicaJ environment. Hants, for instance, require 

j 16 elements for normal growth, 13 of which come 

| tram the soil. Plant tissue analyses may show the 

tresence of many times this number of elements. 

Vegetation forms an important node and link in 

| to transport and distribution system of lead enteral the environment from mining, mining, and smelting processes. The residence time may be quite 

•hart or relatively long. Lead deposited on the 

ewes of trees moves to the soil system with annual 

leaf fall or may be washed to the ground by rainfan. 

Leaves may be eaten by herbivores, thus introducing attendant lead into natural food chains. When 

deposited on forage crops, lead may be ingested by 

domesticated animals. Deposits on leafy vegetables 

may be directly consumed by humans. Plant roots 

also absorb lead from the soil solution, and it may 

be transported and stored in other plant parts. Lead 

incorporated in the woody tissues of a tree might 

remain for marry years. In contrast, that in the edible portion of a radish would be transferred to another node in a matter of weeks. 

Lead accumulations on or in plants growing near 

mines, mills, and smelters have caused problems in 

many countries. (25-25] In Missouri, lead poisoning 

was diagnosed as the cause of death of several horses pastured in the vicinity of a lead tmelter Bt Clover. There is, therefore, an obvious need to monitor 

vegetation for the possible accumulations of lead 

and other heavy metals, especially in the vicinity of 

industrial operations. - - _. . 

The distribution of lead in vegetation of the New 

Lead Belt has been investigated in three general 

areas: 

(1) Lead deposited on the leaves of natural forest 

vegetation near mines, mills, and smelters. 

(2) Lead deposited on vegetation along main haul 

roads arid transport routes. 

(3) Lead accumulated by vegetable crops grown in 

areas where potential contamination is high. 

Lead Accumulated by Vegetation Near Mines, 

Mills, and Smelters 

Industrial operations in the New Lead Belt are 

surrounded by forests. The accumulation of lead by 

some of the important overstory and understory • 

species was investigated during the summers of 

1971-1973. These induced while oak (Qucrcus a/be 

L ), post oak (QUerrus steBat* Wangenh.), short-leaf 

pine (flr'nus enctvnata Mill.), and dryland blueberry 

(Vaccinim pallidum Ait.). 

Post oak and pine foliage were sampled intensively in the vicinity of the .AMAX smelter, while oak 

and blueberry leaves were collected systematically 

over a 12 mi by 23 mi area that included most of the 

Viburnum Trend in the New Lead Belt. Soil samples 

were also taken at the same location as the white 

oak and blueberry foliage. All samples were analyzed without prior washing for lead, copper, cadmium, zinc, and manganese by atomic absorption 

spectroscopy. Thus unless otherwise stated, the results represent internal as well as surface accumulation. 

Unusually high levels of lead were found in and 

on leaves of post oak and short-leaf pine near (0.5 

mi or less) the AMAK smelter, (tabic 7-13) The 

maximum values were 8,125 and 11,750 ftg/g for post 

oak and pine, respectively. Elevated levels of lead 

were detected at distances greater than 2 mi. 

Lead accumulated by white oak and blueberry foliage from the 12 mi by 25 mi sampling area is 

shown in figures 7-18 and 7-19 and tables 7-14 and 7-

149 

; i 
TABLE l-M.-Concentratlon of lead tn leaves of post oak (Qnerens stellate) and needles 

of short4eaf pine (Pimis ediirrata) bt eternity of lead smelter operations 

Dtstance rrom 

smelter (mO 

Lead concentration Qig/g dry weight) 

Range of Standard 

values Mean deviation 

Short-teaf pine 

Lead concentration Qig/g dry wcrtwll 

Range of StanasiT 

values Mean devenjoa 

0-OJ 

0J-1.0 

1.0-1.5 50-1.580 

IJ-2.0 45*40 

More than 2.0 18-1.360 

23041.123 3.776.70 

713.800 771.40 

250.00 

192.80 

168.97 

4.032.2 

777.36 

273.2 

145.8 

222.8 

420-11.750 

101-1.475 

52-1,050 

62412 

22461 

3.546.36 

497.37 

273.56 

142.85 

123.29 

3.312.(3 

366.51 

21617 

178.4) 

125.4) 

TABLE 7-14. -cbfteenrranton of teed or reeves of white oak (Querns alba) and teases of 

blueberry (Vacctntum pallidum) M rkottry of lead tmelter operations 

Lead concentration (»g/g dry sretght) 

Blueberry 

Lead concentration (*ig/g dry weight) 

Distance rrom 

smelter (mi) 

Range ot 

values 

Range of 

values Mean 

2-3 

34 

4-5 

5-6 

75.8-1.221.0 374.3 

122.0- 537.0 2990 7 

39.8- 155.0 80.1 4 

28.2- 276.0 93.0 10 

23.5- 228.0 75.6 12 

26.0- 121.0 54.5 9 

141.W74.0 495.3 

93.0-338.0 203.9 

21.0-146.0 76.1 

34.2-181.0 68.6 

24.0-155.0 • 64.3 

29.0-101.0 41.6 

1

 n * number of samples. 

15. In tbe northern half of the study area, the tmelter was found to be the primary source of contamination, although the influence of mines and mills is 

evident, (figs. 7-18 and 7-19) Additional vegetation 

and soil contamination undoubtedly resulted from 

ore haulage by truck and railroad. 

The Fletcher Mine and mill complex was perhaps 

the primary source of lead contamination in the 

southern half of the study area. 

Leaded motor fuel and truck toansportatton of 

lead ore were also contributing factors. The accumulation of lead by. vegetation was not as elevated Hi 

the vicinity of mines and mills as around the smelter. The distances at which anomalous levels of lead 

occur were also less than in the vicinity of a smelter. 

The amount of lead accumulated by white oak 

leaves was slightly higher than that accumulated by 

blueberry foliage. This slight difference is perhaps 

due to the fact that the blueberry is an understory 

species subject to less aerial deposition than (he 

overstory oaks. 

Elevated levels of Cd, Cu. and Zn (figs. 7-20 and 

7-21) were associated with leaves in the vicinity of 

the industrial operations and were correlated wMt 

lead levels. Manganese levels were high (over 3,000 

Hgjg in many instances), but were not correlated 

with the contamination by Pb and other heavy metals. Manganese is readily available for uptake by 

plants in the acid soils of the area. Cadmium leveb 

ranged from <0.50 to 4.0 jig/g for the SI6 white oak 

and blueberry leaf samples. High levels of Cd were 

found in the samples of leaves containing high kven 

of Pb. In these high lead samples, Cd ranged from 

0.23 to 2.4 jtg/g, with only a few samples greater 

than 10 *ig/g 

Lead Contamination Along Roadways 

Numerous studies have shown that soil and vegetation near highways contain elevated levels of lead 

TABLE V\i.-Concentration oflead In leaves ofwhite oak (Querent •tba) and leaves of 

blueberry (Viccintum pallidum) tn vkattty of Fletcher mine and mtV 

Distance from 

road (mi) 

0-1 

1-2 

2-3 

3-4 

45 

5-6 

White Oak 

Lead concentration (ug/g dry weight) 

Range of 

values 

39.0 

16.5- 70.0 

20.0- 26.5 

10.8- 57.7 

12.5-124.0 

12.5 36.3 

Mean 

39.0 

35.9 

22.6 

20.7 

29.5 

22.6 

n 

, 

6 

6 

10 

15 

II 

Blueberry 

Lead concentration Goj/g dry wesgbt) 

Range of 

nlues 

39.0-132.0 

16.5- 40.0 

16.5- 27.5 

11.3- 42.3 

5.8- 73.9 

5.9- 24.0 

Mean • 

B5J ' 

25.8 > 

20.6 1 

20.6 II 

27.1 » 

17.7 11 

i=n umber of tamp!**. 

150 

-l decrease with increasing distance from the highly 125-32) Some of the elevated levels have been 

^BKt} to result from the use of leaded motor 

H new source for roadside lead deposits has been 

Med along the highway or railroad system in the 

„ Lead Belt, where large quantities of lead, zinc, 

d sometimes copper concentrate are hauled by rail 

, track to the smelters. Although some of the lead 

otaitrate is smelted near the mines and mills in 

northwest Iron County, a major portion is etther 

shipped by rail to a smelter near St. Louis or hauled 

by truck and smeltered in southeastern Iron County. 

The haulage trucks may or may not be covered, and 

the combination of open trucks, rough roads, and 

wind results in considerable blowing and deposition 

of the ore concentrate on roadside soils and vegetation concern about the hazard from open-truck hauling was heightened when unusually high concentration of lead, copper, zinc, and cadmium were.reportLEAO M WHITE OAK LEAVES 

•42.6 

"GITO 7-ta.—Lead In white oak leaves 

1S1 
152 

LEAD IN BLUEBERRY LEAVES 

RGURE 7-10—Lead In blueberry earns. 

CADMIUM IN WHITE OAK LEAVES 

fBUfiE 7-20.—Cadmium In white oak reave*. 

153 
CADMIUM IN BLUEBERRY LEAVES 

RGURE 7-21.—Cadmium in blueberry 

I in red cedar (Jimiperus vtnjpmana, L.) foliage 

^ haulage routes near Centerville. (33) These 

ere thought to reflect vehicular transport of leadaring ores, rather than mineralized rock. An mtenrt sampling of both soil and vegetation was initiatI to determine the extent to which areas adjacent 

, the highways were being contaminated by the 

sjjsport of lead concentrate from mines and mills 

i the smelter. 

The main haulage routes are shown in figure 7-22. 

rfand vegetation samples were taken at approxiatety 3 mi intervals beginning at Glover. Control 

pnples were collected southward (samples 73 to 80) 

[ the southern-most mine of the Viburnum Trend in 

Reynolds County, westward into Dent County (samples 127 to 134) from the smelter and mine near 

Bixby (northwest Iron County), and north of the 

main truck routes (samples 135 to 142) into Washington County. The area traversed by the trucks varies 

from relatively open cultivated or pasture lands to 

dense oak-hickory-pine forests. 

In open areas, samples of soil and vegetation were 

collected at the roadside and at distances of 100, 

200, 300, and 400 yd from the roadway. In densely 

wooded areas, sampling was limited to the road 

right-of-way and, where possible, at least 100 yd 

into the forest. Since no one vegetation species was 

present at all sites, some were collected during July 

•two * 

WASHINGTON COUNTY 

«>o.a. 

'GWE 7-22.—A representation ot levels of toad lo vegetation 

**g lead or* truck routes (solid lines) and control routes 

**m lines). 

• <7pp«.LEA0 AMWESftMIUS 

» " 7-70 ppm LEAD m SMELTERS 

•>70ppmLEA0 -> TRUCK ROUTES 

© CONTROL ROUTE 

iiti\\ytrtxt\OOf^fra^\^rot3d 

3rd symbol 300 yda from ma rood 

155 

TJ 
i« 

! 

I 

If1 

and August of 1970: fall fescue (Festuca arundinacea 

xchreb). a domesticated forage species that is also 

extensively seeded on highway rights-of-way; purple 

top (Tridcns flaws L. Hitch), a native grass species; 

and dryland blueberry (Vacdnium pallidum). Purple 

top was the most common species. Additional samples were collected during the summer and early fall 

of 1971 along a series of transects at distances of 25 

to 1.000 ft from the main roads. Lead ore has been 

transported over most, hut not all, of these routes. 

Grass plants were severed approximately I tn. 

above the soil line, and all visible soil particles were 

brushed from the base of the plant prior to analysis. 

Mature leaves of blueberries were taken from the 

center one-third of the current season's growth, 

while oak leaves were collected from branches approximately 6 ft above the ground. The vegetation 

samples were not washed prior to analyses. 

Soil samples were collected to a 6 in. depth with a 

soil auger. Soil samples were extracted with 0.2 percent acetic acid for 2 h to determine available lead. 

Total lead values were determined by digestion with 

concentrated nitric acid. 

Analyses of vegetation samples from the truck 

and control routes are given in table 7-16 and 7-17. 

Lead concentrations associated with plants along the 

haul roads varied markedly among individual sampling sites. The highest levels were in samples collected near smelters, mines, and mills and along 

rough areas in the highway surface that caused the 

truck transports to bounce. Lead content decreased 

rapidly as the distance from the roadway increased. 

TABLE 7-lt.-ConcentratIon of lead In vegetation 

along nn truck routes 

Distance from mad 

right-of-way (yards)1 

0 

100 

200 

300 

400 

0 

100 

0 

100 

200 

300 

400 

0 

100 

200 

300 

4 0 0 

Lead concentrstlon Oig/g dry weight) 

Lnw Mean 

All Specie* 

1.0 

1.9 

2 4 

4.8 

4.0 

279.7 

34.2 

1 1 6 

8.5 

6.5 

Blueberry 

7.0 

10.4 

98.0 

45.0 

Fe«ue 

20.0 

4.9 

7.3 

1.5 

6.9 

Purple 

1.0 

1.9 

2 4 

4.8 

4.0 

341.0 

9.6 

10.6 

10.0 

8.0 

Inp 

344.0 

32.0 

12.0 

7.6 

5.8 

High 

4.350.0 

537.0 

35.0 

15.0 

9.1 

537.0 

172.0 

915.0 

14.3 

19.0 

15.0 

9.1 

4.350.0 

537.0 

35.0 

10.1 

8.3 

«' 

80 

S I 

16 

8 

6 

21 

22 

3 

8 

5 

3 

2 

56 

28 

I I 

5 

4 

1

 n= number of .ample*. 

156 

TABLE I'M .-Concentration of lead tn vegetation 

along control routes 

Drilance from road 

right-of-way (yards) 

• Lead concentration Qig/g dry wejuhn 

Lnw Mean High „• 

mce from road 

Surf-way lyardi) 

0 

100 

200 

300 

4 0 0 

24 

0.15 

18.1 

8.1 

7.2 

3.9 

3.9 

49.0 

20.0 

12.0 

5.8 

5.8 

10.0 

0.15 

17.3 

10.7 

49.0 

18.0 

100 

200 

300 

4 0 0 

18.2 49.0 

7.4 18.0 

7.2 12.0 

3.9 

3.9 

'n=numbet of sample*. 

- Lead .levels. were_ several times higher along ore 

transport routes than on control roads. 

Elevated levels near control highways probably 

reflected contamination from leaded gasoline. Also, 

the Missouri Highway Department occasionally 

spread slag from the smelters on highway shoulders, 

but this practice has been discontinued. Levels in 

plants approached background levels beyond 200 yd 

from the roadway. 

Lead added to soil in a soluble form soon changes 

to unavailable or fixed forms. It was desirable to 

determine whether there was a better correlation 

between the plant levels and soluble lead, as idicated 

by extraction with 0.2 percent acetic acid for 2 h, or 

between plant levels and total lead determined by 

digestion of the soil with concentrated nitric acid. 

The concentration of soluble or theoretically available lead in soils along the ore-truck routes is shown 

in table 7-18 and along control routes in table 7-19. 

Marked differences were evident between (he tntdt 

and control routes near the road, and a severaMoM 

difference at greater distances from the road. 

The total lead contents of the soil are shown in 

table 7-20 for ore-truck routes and for control routes 

in table 7-21. A 10-fold difference was evident in 

TABLE 1-1%.-C(*neentratton ofavaHablr leadtn 

mils atrmg ore truck routes' 

'SoBs collet ted lo A tn. depth. 

'.-oombef or umptes. 

pptes collected on the road right-of-way. Later 

ofies by Bolter et al. |34] have shown that lead 

net titrations are greatest in the organic layers or 

e top few millimeters of mineral horizons in undiluted soils. Much higher values were attained once 

tst fractions were analyzed. 

The accumulation of lead by all plant species is 

own in figure 7-21. Vegetation containing more 

ni 70 /ig/g lead (dry weight) denoted by the bold 

xk circles was located only on road right-of-ways 

mg truck routes. Near mines, mills or smelters, 

TABLE 7-20. - Total lead In toils along truck routes' 

Met from road 

M-of-wiy (yirdrt 

right-of-way lyardi) 

0 

100 

200 

300 

4 0 0 

Lead concentration tng/g dry weight) 

U w 

0.09 

0.01 

0.03 

0.02 

0.04 

Mean 

17.54 

0.45 

0.75 

0.S6 

0.85 

High 

133.0 

4.5 

6.6 

2.9 

3.8 

a* 

Si 

46 

11 

9 

> 

'Soil umpk i collected In * in. depth. 

' n number of .ample*. 

TABLE 7-l9.-Onren/ref4on of soluble available lead In 

totts along coneot rmitet1 

Lead concentration (pg/g dry weight) 

0 

100 

200 

300 

400 

0.08 

0.19 

0 0 4 

0.15 

0.15 

0-38 

0.46 

0.27 

0.25 

0.28 

3.80 

1.40 

0 3 0 

0.40 

0.50 

24 

16 

Leed concentretion Oig/g dry weight) 

Low Mean High « ' 

100 

200 

300 

400 

16.7 

12.7 

20.0 

330 

36.0 

809.6 

32.5 

36.0 

52.0 

55. 0 

3.792.0 

80.0 

48.0 

55.0 

176.0 

'Sao lampki collected to « hi. depth. 

'asnnmtier of lamptei. 

rets were more elevated at 100 yd or more from the 

id-right-of-ways. 

Concentrations of lead in white oak and blueberry 

rets along ore-haulage and control roads are 

own in tables 7-22 and 7-23. There is good agreeent between values obtained for the two species, 

tad levels decreased with increasing distance from 

i road, but were still elevated at 1,000 ft from oretsage routes. Some lead may also blow onto the 

abide vegetation from smelters, mines, and mills. 

as the absolute amount of contamination due to 

x haulage cannot be determined. 

TABLE 7-2l.-7b'aflreefrnB>ffsetonjeonm>fitMrtrs' 

e from road 

PJ-of-way (yards) 

Lead concentration Oig/g dry weight) 

Low Mean High n ' 

100 

200 

300 

400 

10.7 

9.3 

8.3 

13.3 

13.3 

756 

23.2 

17.3 

17.3 

22.0 

384.0 

49.0 

27.0 

20.0 

33.0 

Sag umptcs collected lo A tn. depth. 

'n=oonih*t of tempi... 

The importance of ore transport at a source of 

contamination is illustrated by data from the pasture 

where problems with horses were encountered. 

Samples of forage grasses, collected in July approximately Vi mi north of the smelter, had a lead content 

of 115 sig/g dry weight nearest the smelter, 344 ug/g 

at 100 yd from the southern edge, and 1,140 iig/g at 

the northern edge, which was immediately adjacent 

to the highway used to transport lead ore to the 

smelter. 

Lead Accumulation by Vegetable Crops 

Although lead mining, mining, and smelting operations have been carried on for over 100 years in 

seven southeastern Missouri counties, only recently 

has concern arisen over possible contamination of 

fruits and vegetables grown in the area. Elevated 

lead levels found in miscellaneous fruit and vegetable samples in June and July 1970 emphasized the 

need for a more thorough investigation of toxic metals in crops used for human and animal consumption. In response to this need, a study was Initiated 

to determine the accumulation of lead in leaf lettuce, 

radishes, and green beans grown near sources of 

contamination. |35J These three crops, were chosen 

'because'they' are'commonly grown, and'each represents a different edible plant part. Control samples 

were collected in three north central Missouri counties, well removed from any known lead deposits or 

associated mdustrial operations, and away from 

heavily traveled roads. AD samples were obtained 

from home gardens. 

The vegetables were harvested at the edible stage, 

and samples were immediately washed in distilled 

water. For analytical purposes, lettuce was divided 

into roots and tops, radishes into edible roots and 

tops, and greenbeans into pods and roots. Ties results of the analyses are shown in tables 7-24, 7-25. 

7-26, and 7-27, respectively, for control counties. 

Ok) Lead Belt counties. New Lead Belt counties, 

and a small town located within 2 mi ot a smeller 

that has operated since the 1890's. 

Mean lead levels were generally much greater for 

plants grown hi gardens subject to contamination 

than in the controls. Considering only the edible 

plant parts, accumulations were greater for lettuce 

leaves than for radish roots or greenbean pods. Variations in lead values for individual samples were 

great and were related to the degree of exposure. 

In the Ok) Lead Belt, samples of lettuce and radishes with very high lead contents were grown near 

ok) mines or on soils where dolomitk limestone 

mine waste had been applied to gardens. In the New 

Lead Belt, lead values depended on the proximity of 

gardens to industrial operations or haul roads with 

the highest levels near smelters. 

Exposure to smelter emissions in the small-town 

gardens produced the highest lead levels recorded 

for lettuce and greenbeans. The values for lettuce 

ran as high as 1.324 ug/g. about two times greater 

than elsewhere. Lead values in greenbean pods 

ranged up to five times higher than did values in the 

157 
H: 

TABLE 7*22.-Conwnrmrfcm of lead tn leaves of whae oak (Quercut alba) and leaves of blueberry 

(Vacclntum pallidum} from traverse samples along roads in Missouri's New Lead Belt 

Distance from 

road (ft) 

0- 50 

5 1 - 100 

101- 200 

201- 40 0 

401 - 600 

601 - 80 0 

801-1,000 

white oek 

Lead concentration (ug/g dry weight) 

Range of values Mesn n' 

69.0*04. 0 

32.2-495.0 

21.7436.0 

12.0-286.0 

13.0-293.0 

11.0-113.0 

9.8- 66.5 

209.0 

149.0 

115 3 

81.6 

78.9 

42.3 

53.4 

15 

21 

30 

26 

23 

I I 

I I 

blueberry 

Lead concentration 

Range of values 

47.0-524.0 

21.1-419.0 

14.6-322.0 

11.9-351.0 

17.5-259.0 

5.0-137.0 

5.0-111.0 

(ng/gdryweitlit)' 

Mean .< 

200.7 |t 

176.8 11 

103.0 a 

92.9 n 

79.1 n 

46.3 1) 

34.9 | | 

* f.=nttmber or tamptaa. 

TABLE 1-2i.-Concentration of lead in leaves of white txk (Quercui alba) and leaves of blueberry 

(Vacclntum pallidum) from traverse samples along roads 

without lead ore haulage In Missouri's New Lead Belt 

Distance from 

read (ft) 

0- 50 

5 1 - 100 

101- 200 

201- 40 0 

401 - 60 0 

601 800 

801-1.000 

white oek 

Lead concentrstlon (jig/g dry weight) 

Range of values Mean ni 

52.4.104.0 

34.3- 45.8 

21.7- 26.6 

12.0- 19.8 

17.5 

11.6 

9.8- 14.9 

8 1 0 

41.3 

24.5 

16.3 

17.5 

11.6 

12.0 

' J 

3 

4 

4 

1 

1 

4 

blueberry 

Lead concentration (ug/ g dry weietill 

Range of values 

47.0-100.0 

21.1 44.7 

19.5- 43.7 

11.9- 30.0 

19.1 

12.1 

12.8. 22.2 

Mean •• 

69.2 ] 

29.2 i 

32.4 4 

20.2 4 

19.1 1 

12.1 1 

16.7 4 

I Lead Belt and three times higher than those in 

, New Lead Belt. |3tS] 

Lettuce roots had higher mean lead concentrations 

i either radishes or greenbeans. The highest valsure in the smelter town, where concentrations 

coded 3.000 itglg and averaged 636 ug/g. 

rhe effects of these high lead levels on human 

,tlh have not been determined. However, the vegftles analyzed do not constitute a major part of 

, Set tor people in the area. Thus Ihe possibility 

ctarnic effects is somewhat lessened. 

LEAD IN SURFACE WATERS 

Research studies were performed to determine the 

parlance of surface waters and aquatic systems in 

i New Lead Belt area as a possible sink, a trans-

' "X 

1

 n=number or umples. 

TABLE 7-24. -Lead content of vegetable crops 

tn control counties 

TABLE 7-26. -Lead content of vegetable crops In 

New Lead Belt counties 

Crop 

Lcttuce-fnot 

Lettuce-leaf 

Radah-rnot 

Radrth-lop 

Grccnbcan-root 

Grcenbcan-pod 

Lead concentration (ug/g dry 

Low High Mean 

10.0 

6.9 

5.0 

5.0 

5.0 

<5.0 

50.0 

33.9 

11.0 

32.0 

20.0 

<5. 0 

20.3 

20.6 

7.7 

14.0 

9.1 

<5.0 

weight)1 

12 

12 

12 

12 

12 

12 

Crop 

Lettuce-root 

Lettuce-leaf 

RadKh-root 

RadWHop 

Crccnbearwoot 

Green hcan-pod 

Lead concentration (ug/g dry wriest)1 

Low 

10.0 

8.9 

4.4 

13.3 

5.0 

5.0 

High 

660.0 

923.0 

107.0 

578.0 

53.0 

40.0 

Mean a' 

89.7 21 

114.0 » 

22.3 11 

94.4 a 

9.9 21 

8.8 21 

1

 All umplaJ. washed in dhitlled water im medial fly after harvett. 

't^ftumhrr of larnpUs. 

TABLE 7-25.- Lead content of vegetable crops 

vt Old Lead Belt counties 

1

 All aamntc* washed in dittltled water immediately after harm!, 

'n^number of tamplei. 

TABLE 7-27. -Lead content of vegetable crops m 

a small town with a lead smelter 

Crop 

Leltuce-rnot 

Lettuce-leaf 

Radish-Toot 

Radrth-lop 

Green bean-root 

Cirecn bean-pod 

Lead concentration (ug/g dry weight)1 

Low 

11.7 

10.3 

5.0 

5.0 

5.0 

5.0 

High 

492.0 

742.0 

518.0 

117.0 

67.0 

10.1 

Mean 

68.8 

83.8 

33.4 

76.7 

8.6 

5.4 

n* 

30 

30 

30 

30 

30 

30 

Crop 

Leitucc-ront 

Lettuce-tear 

Radrdwo.it 

Radish-top 

Giccnhean-rnot 

Grccnbcan-pnd 

Lead concentration (ug/g dry weight)1 

Low 

25.0 

47.0 

7.4 

32.0 

10.0 

5.0 

High 

3.244.0 

1.324.0 

50.0 

385.0 

704.0 

136.0 

Mean a' 

636.2 I 

284.0 ' 

22.3 » 

119.5 » 

119.3 • 

25.1 < 

1

 All tampln wa-hed in do tilled water immediately after harveit. 

*n=numher of urn pies. 

1

 All ".ample" washed in Untitled water immediately after ttarml. 

'n=numb*r of «mple-. 

158 

port mechanism, a habitat for fish and other aquatic 

organisms and a recreational resource. (371 

The topography and resulting drainage pattern of 

the New Lead Belt are uniquely adapted to monitoring and tracing the effect of industrial pollutants. 

First, the mining, milling, and smelting effluents 

from each operation are channeled into separate 

stream systems, so that any pollution effects can be 

individually determined. Equally important are the 

many streams without mining development that 

serve as controls. Five of the streams receiving mine 

discharge eventually flow into the Black River basin 

and then into Clearwater Lake (approximately 70 mi 

away). This is the only lake in the system and potentially a major long-term sink for heavy metals entering the system. A map of the basin, emphasizing the 

overall drainage pattern, is shown in figure 7-23. 

\ 

9JRE 7-23.-4>atnag* partem of Belt of Mhaoui to Clearwater Lake). 

159 
Source

s of Pollutants 

The primary sources of heavy metals are mining 

and milling operations, concentrate storage, haulage 

by open-truck or railroad gondola car, and the smelt-

ing operations. Generally, however, wastewaters 

from mine and/or mil) operations are the most im-

portant to the aquatic systems, although they do not 

normally enter the stream systems until they have 

been treated in at least a single tailings pond. The 

liquid effluent from these ponds is not chemically 

too different from the receiving streams, but it does 

contain relatively large amounts of suspended solids, 

which are generally associated with heavy metals. 

Effluent from the mining operations often contains 

approximately two to three times more dissolved 

solids than either the original mine or background 

stream water. (38] 

Organic reagents are also released by the mining 

operations and may become major environmental 

problems. Many of these materials are known to be 

toxic in aquatic systems, but the levels at which tox-

icity occurs, particularly in the presence of heavy 

metals, are not known. [39] A summary of factors 

contributing to environmental changes in water qual-

ity are listed as follows: 

A. Mine water 

1. Natural nutrient load of subterranean water 

2. Fuel spills 

3. Oil spills 

4. Hydraulic fluid spills 

5. Small mineral particles in mine effluent 

6. Blasting agents—spills and partially oxidized 

compounds are nutrients 

7. Highly variable mineral content of ore 

B. Mill operation 

1. Chemical spills 

2. Variable mineral content of ore may cause: 

a. Excessive use of reagents and loss of toxic 

chemicals to effluent 

b. Low recovery of heavy metals during 

pulse of very rich ore 

3. Chemical reagents not adsorbed to concen-

trate are released in effluent 

4. Improperly placed piles of concentrate allow 

dispersal of heavy metals 

C. Tailings ponds 

1. Improper design or placement of ponds, in-

sufficient size or number of ponds 

2. Insufficient retention time 

3. Release of toxic milling reagents to streams 

4. Release of organic and inorganic nutrients to 

streams 

5. Release of finely ground rock and mineral 

particles to streams 

Research Procedures 

Heavy metal concentrations in the water (both 

dissolved and suspended states), stream sediments, 

and the aquatic biota were determined by atomic 

160 — 

absorption methods as described in a previous chap, 

ter. Routine analyses were made by the Environ 

mental Trace Substances Research Center at fe 

University of Missouri. Some analyses, largely cotv 

cemed with stream biota, were performed at Rod, 

using standard techniques coupled wilh occasion) 

blind cross-checks between the two analytical bbr> 

ratories. 

Dissolved and suspended matter were separated 

by using a 0.45 nm Millipore filter; all water (ha 

passed the filter was assumed to contain essentially 

dissolved material. All physical and chemical pan-

meters of water quality were determined in accord. 

ance with procedures outlined in standard methods 

of the American Public Health Association, |40| 

except for phosphorus determinations. Both totd 

and orthophosphate were measured with procedures 

developed by Jankovic et al. (41] Diversity Inde-

values, cited as the biological indicators of pollution. 

were measured by Ryck and Whitely [42] of the 

Missouri Department of Conservation by usht 

Wilhm's expression: [43] 

Diversity Index = \ |No

. of'type type! s of Organisms)-! 

(tota ota

l n l no

. of organisms!" 

There are numerous shortcomings in the use d 

indices because most are distorted in some way and 

generally concentrate on one or more organism*, 

Wilhm's index is mathematically distorted to favor 

certain fly larvae that are carried to the species level. The index does not necessarily indicate a decline in the number of life forms, but rather a change in 

the basic character of the original taxonomk group* 

ings. As such it is valuable only as a guide to indi-

cate that changes have occurred. (44, 43] 

The establishment of basic rainfall and runoff 

characteristics was in accordance wilh current hydrological practices. Two Leupold and Stevens sovomanometer bubble gages were used to measure 

streamflow. Water samples were collected at 15 min. 

intervals during runoff periods. Both filtered an) 

unfiltered aliquots were analyzed for lead, copper, 

zinc, and cadmium. Other water quality characteris-

tics measured included pH. hardness, alkalinity, 

chemical oxygen demand, and many others. 

Analytical procedures for algal analyses were detailed in a previous report. (371 Briefly, algae samples were dried at lOOX and ground. Approximately I g of the dried material was digested in a 100 ml 

Kjeldahl flask with IS ml concentrated HNOj and) 

ml concentrated HCLO4 until the white fumes of the 

perchloric acid were evident, followed by an addi-

tional 5 min. at the lowest setting of a Kjeldahl heal-

ing unit. The digested sample was picked up in • 

percent HNO3, and the washings were added to the 

supernatant. The liquid samples were brought to 30 

ml with I percent HNO3 and analyzed for heart 

metals by atomic absorption spectroscopy. Stand-

ards and blanks were prepared with I percent 

HNOj, and the results were expressed in terms d 

micrograms of heavy metal per gram of dried algae. 

pad on Water Quality and Aquatic Biota 

ffaier Quality: Most of the lead from mining and 

iffing operations enters the streams as galena 

kjjS), In addition, small amounts of lead oxide 

•X)). lead carbonate (PbCOj), and lead sulfate (Pb-

\)A) may also be found. Little is known, however. 

out the chemical alterations and eventual assocta-

gns of lead as it reacts with organic substances 

tsetit in and around aquatic vegetation. (46] Be-

it mining began, background concentrations of 

id and copper in streams of the New Lead Belt 

oe reported to be in a 4 to 6 pg/l range; water p H 

rrged normally between 7 and 8. [46] 

hysical and Chemical Impact 

A summary of the physical and chemical parame-

n of water quality at IS selected principal sam-

Sng stations is presented in table 7-28. The most 

.gnjncant differences in observed values of chemi-

i and physical characteristics of the control 

rcanis and those receiving industrial effluents are: 

(1) The turbidity and suspended solids levels 

found in samples taken at or near industrial 

outfalls are far higher than those found in the 

receiving stream; as a general rule, the-heavy 

metals are associated with these solids. 

(2) Mine-mill effluents generally have a markedly 

higher level of total dissolved solids relative to 

the control and receiving streams. [38] 

(3) Periodic elevated levels of phosphate and ni-

trogen are found in stream segments with oc-

casional algal blooms or aquatic vegetation. 

(4) Most of the available phosphorus and nitrogen 

are commonly tied up either by aquatic biota 

or dissolved organic compounds, many of 

which are probably metabolic products of tbe 

stream biota. Organic nitrogen (Kjeldahl analy-

sis) consistently accounts for over 99 percent 

of the total nitrogen present. 

(5) Under normal stream Row conditions, most 

streams of the New Lead.Belt are remarkable 

for their high degree of clarity, purity, and 

aesthetic qualities. 

During normal flow, both dissolved and suspended 

ad contents of the water were well below the 0.05 

•t/l level set for drinking water by the U.S. Public 

fadth Service and the 0.1 mg/1 effluent standard set 

ir the Missouri Clean Water Commission for this 

|pe of discharge. |44] Since streams in this region 

taracteristtcally have a relatively high carbonate 

intent and a slightly basic pH [47], any dissolved 

ttvy metals are probably precipitated rapidly as 

osoluble carbonates. Since most of the particles are 

arty colloidal in size, they are likely to be trans-

Wted and deposited in a reservoir or any other 

•Vatic body that provides long-term sediment con-

Dions. It is significant that virtually all of the high 

ftasurements of heavy metals occurred during per-

odi of storm runoff and are associated with the 

vspended solids fraction. This Dhenomenon has not 

*tn noted in most conventional monitoring pro-

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jars near the AMAX smelter during storms; its pH 

averaged around 6. During periods of peak runoff, 

the stream pH normally varied slightly. Thus it is 

not surprising to find that increases in dissolved 

metals were very small. According to Foil, [55] up 

to 5 to 6 mg/1 of the total 25 to 30 mg/1 lead occurring during peak runoff periods associated with large 

storms are in a dissolved form. The interesting point 

is the abrupt major increase in the metal content of 

suspended solids. 

Anomalous cadmium values were also found in 

the runoff from the smelter watershed. This was 

unexpected, since il rarely occurs, in natural waters 

of the region. Small amounts of cadmium were present in the lead ore. hut that occurring in the smelter 

solid wastes, lagoon effluents, and leaf litter surrounding the smelter appears to he abnormally high. 

Similar relationships exist for zinc and copper iii 

unfiltered runoff, indicating (hat runoff is a major 

transport mechanism for all heavy metals. 

Lead in Stream Sediments 

The relatively large amounts of suspended heavy 

metals found in streams during storm runoff pose a 

question as to whether they come from material 

washed in from the soil or from a resuspension of 

sediments on the stream bottom. 

I Investigations have shown that stream sediments 

c the New Lead Belt contain relatively low levels 

4 lead and other heavy metals, and these concentrapons are only found near effluent sources. Most of 

tbe lead generally occurs in the range of 200 mesh or 

jter. This is not unusual since 90 percent of the ore 

|s ground finer than 200 mesh. In addition, the mintrals containing heavy metals are generally more 

'(riaMe and may be crushed even finer. Also, there is 

'rirtually no clay in the stream sediments (based ei-

'iher on particle size or geochemical characteristics, 

'even though soils of the region characteristically 

[contain from 9 to 15 percent clay). Clay materials 

jare obviously being carried in suspension by the 

oalx crtbo tdoo obo i-fco raco abo 

Stam 2,34»X 11,074 

FIGURE 7-26.—Metal content of emetter runoff. 

n%m,kvt 

Storm 7, Jan. 0,1975 

164 

stream water. Thus heavy metals associated with 

suspended solids during runoff appear to be washing 

directly from the soil to the streams, and thence 

move out of the ecosystem. This transport mechanism has been reported by studies earlier in Missouri, 

[49] in Illinois. [56] and elsewhere. [57. 58] 

In one particular case, extraordinarily high lead 

levels (t 11,000 pg/g) were found in sediments near 

the ASARCO smelter at Glover, MO, just outside of 

the New Lead Belt, (table 7-29) This materia) 

reached the stream following attempts to reduce 

plant dust in compliance with requirements of the 

Occupational Safety and Health Act. The attempts 

involved installation of a sprinkler system that periStorm 9/0,Wl24/»ttOTS 

FIGURE 7-27.—Mvtal content of smelter runoff. 

185 
grams since most state and federal agencies regularly use filtered samples for analyses of heavy metals. 

One important rinding is that lead has rarely been 

a problem in the effluents or in streams; however, 

zinc has frequently exceeded the 0.1 m/gl limits required by the state in both filtered and unfiltered 

samples. [37. 44-45] The highest concentrations of 

heavy metals have consistently occurred at stations 

16 through 20, which are essentially effluent discharges from the smelter treatment facility. These 

are also the only stations where cadmium is regularly found, and heavy-metal concentrations in unfiltered samples at these sites consistently exceed the 

state's allowable limit. These effluents drain into a 

basin that has been studied under storm runoff conditions and will be discussed in another section. 

BWoRlc*d Impact: The effluent from mills and excess mining water continually pumped from the 

Bonneterre formation have exerted a definite impact 

on the productivity of small receiving streams. The 

amount of water that must be brought to the surface 

varies considerably from one .mine to another, ranging from almost nothing to approximately 4,000 gal./ 

min. 

In those operations with an excess of underground 

water, algal blooms have occurred in some of the 

tailings ponds used for'treatment and for several 

miles below the discharge point in receiving streams. 

These algal growths and associated rhizophytes 

(rooted vegetation) vary in species composition from 

one stream to another; in some cases, they completely cover stream bottoms. Excessive algal blooms, 

particularly in the warm months, have caused an 

unsightly appearance and altered the usual aquatic 

communities. 

The predominant vegetation associated with 

streams that have algal growth problems were: Ctodophora, OscilMoria, Mougeotia. Zygnema, Spirogyra cymbetta, Aehnanthcs. Navicuia, and other 

stalked and nonstalked varities of diatoms. The typical benthic and peri phytic communities display an 

unusually large array of diatoms, both in variety and 

density. These aquatic forms very efficiently accumulate nutrients in streams where their concentrations are quite low. 

The dense, tangled, gelatinous communities of 

algae and associated microconsumers act as excellent filters, in addition to their capacity for nutrient 

removal and retention. The finely ground particles of 

rock flour or minerals that may escape the flotation 

and tailings reservoirs are efficiently trapped and 

removed by the benthic flora of the receiving 

streams, [43, 49] as illustrated by figure 7-24. The 

residence period for these accumulated materials is 

only temporary, since the mats are detached as they 

decompose or break loose during periods of storm 

runoff and are carried by moving water into other 

ecosystems. 

Elevated manganese concentrations have been 

observed in many of the industrial effluents sampled. 

Patrick ef al [50] and Gerloff and Skoog [51] have 

reported thai manganese concentrations, similar to 

those observed on Bee Fork and other streams in 

162 

OWam ftc*. IWfaea Oom (Maa) 

FIGURE 7-24.—Alaad read content—before, after, and within 

the a*o«l meander treatment system. 

the New Lead Belt, may interact with temperatiie 

to selectively favor the growth of some kinds of algae. In particular, high manganese concrntratiora 

and cold water temperatures encourage the development of diatom communities, while the opposite 

conditions lead to establishment of green or bluegreen algae. Thus some of the differences between 

the predominant algal forms in the various recdvinj 

streams are partly due to differences in manganese 

concentrations. 

A potential environmental problem has developed 

in the transport of heavy metals when excessive 

vegetational growths have occurred in the receivini 

streams. These dense gelatinous mats of algae and 

their associated aquatic populations have coated 

some stream beds, causing aesthetic problems, 

blocking photosynthetic energy input, and dimmsting normal stream populations. 

The quality of two typical streams as measured by 

diversity index values are shown in figure 7-25. (42, 

52] Generally, neither a control nor a receivinj 

stream had a diversity index of less than 4 prior to 

the initiation of mining operations. [42] In contrast, 

these index numbers decreased to levels below 4 in 

streams receiving wastewaters after mining «w 

started. The initial drop, as shown m figure 7-23, 

occurred just before the mines started product** 

and was probably related to preminmg construction 

activities. Since then, both the total number ttvA 

type of benthic organisms (as described in Wflrnn'i 

Index) in the receiving streams have declined. Witt 

L URE 7-2S.-Otver-Jtylr^ 

DIVERSITY INDEX - .NOC^ TYPES OFQRGAWSMSl-l 

BstaDation and operation of treatment facilities, 

team water quality as measured by benthic diverstr indices has improved to premining or background 

tvds. It is important to recognize that such selected 

Wogical indices are not indicators of water polluter.. They only indicate that the types and numbers 

tf organisms used to compute the index have 

tanged; as such, they can function as a sensitive 

tool for detecting possible environmental trouble 

nas. 

Lead Transport by Runoff 

The airborne transport of lead from tailings, concentrate piles, transport vehicles, and the smelter to 

Ihe soil tea been previously described. Research furflier suggested that lead is held rather tenaciously in 

tbe organic horizons and the uppermost portion of 

the mineral soil profile. Observations in the Old 

Lead Belt of Missouri indicated that lead levels in 

tbe 0 to 6 in. soil were nearly the same as those m 

(be New Lead Belt 137] This poses a question as to 

whether soil is the ultimate sink for lead or whether 

tbe isolated high values of lead in unfiltered water 

tnrrp.es during periods of high storm runoff might 

be a significant transport phenomenon. 

Soil column studies by Lirmeman 153] indicated 

flat there was very little leaching of heavy metals at 

present levels of contanrinattoti. and that day and 

organic soil fractions have a strong affinity for lead, 

effectively limiting its cVownward movement. Automated runoff water quality stations were also constructed on two watersheds to check this general 

transport hypothesis. The control watershed (approximately 5 mP in area) was located 6 mi from the 

smelter and was assumed to be beyond inputs from 

industrial sources. The other watershed drained a 

IVi miZ smelter area where the primary heavy metal 

input was deposited on the soil. Water samples were 

analyzed for lead, zinc, copper, cadmium, and 11 

other physical and chemical parameters of water 

quality. (37,54] 

Figures 7-26 and 7-27 show rainfall intensity, runoff, and lead values for filtered and unfiltered samples during four selected storms, including targe and 

small precipitation events, on the smelter watershed. 

The total lead content in the smelter watershed runoff is 30 to 50 times that of normal flow and several 

thousand times larger than the control; (37) the differences in basin size are insufficient to account for 

this. Similar patterns exist for zinc and cadmium. 

The coincidence of highest lead concentrations and 

peak runoff suggests that targe amounts of materia) 

are moved during heavy storms. 

Rainfall was collected in wide~mouth polyethylene 

163 
I 

I 

I 

m 

s * • I' 

Bt! 

200 400 600 BOO 1000 1200 1400 WOO 00 0 2000 2200 2400 2600 

ml through column 

RGURE 7-29.—Cation exchange using algae (40 g wet weight Spirogyta), column pretrested 

with 400 mtOt WNaAc. 

Heavy metals are most commonly added to 

streams as sulfides, carbonates, or phosphates — al) 

of which are quite insoluble in the hard, slightly alkaline streamwater of the region. The abundant anionic sites known to be present in cell walls and surrounding matrices provide ample opportunity for ion 

exchange. Electron microscopic studies by Malone 

et al. [65] suggest that when hydroponically grown 

corn roots are treated with dissolved or chelated 

lead, insoluble lead particles appear in isolated 

membrane-lined vesicles within the root cells. Few 

vesicles containing lead are found in stems or 

leaves. More recent autoradiographic studies by 

Rule et al. [66] indicate that some of the lead applied 

to leaves of radishes and lettuce may enter the vascular system and be transported to other plant tissues. The lead that remains associated with aquatic 

vegetation in the New Lead Belt streams appears to 

be bound primarily to the cell membranes of algae, 

based on electron microscopy studies by Wixson 

and Gale. [67] 

Extensive washing of aquatic plant material in distilled, tap, or stream water failed to remove (he 

bound lead. However, washing with EDTA (ethylene diaminetetraacetate) at pH 7 to 7.5 in concentrations as low as 0.01 M effectively removes most of 

the associated lead without cell rupture. (68] Laboratory studies using filamentous algae or leaf litter 

packed in columns determined the capacity of plant 

matter to bind, by cation exchange, soluble lead salts 

tOOO 1*00 MOO 

ml through column 

i 7-30 —Uptake of leed by leaf litter used In column studies. 

168 

40O0C* 

sspocf 

30p«* 

25p0(* 

£ 20jOOC+ 

ispoc* 

lajooojaportdlh wilh 00125 EOTft 

pH7.5 

100 l o o 55b" 40*5 aco Soo TOO" 

. Totol • ml of 100 ppm Pb tn NoAc 

JFCITRE 7-31.—Uptake and release ot lead from mixed culture ot atgae. 

\ • • 

W \80 0 * » tOOO 

fin the presence of abundant monovalent cations. 

!%. 7-29 to 7-32) Cation exchange capacities, based 

Ion the column studies, approached 65 meq/100 g for 

!flamentous algae (over-dry weight basis) and 180 

jneq/100 g for dried forest litter material. The concentrations of lead reported in forest litter [621 and 

Lhose found in aquatic vegetation often do not approximate the total cation exchange capacity of the 

vegetation involved. Control columns using glass 

wool with overlaying lead sulfide (concentrate) indicate vast differences in the leaching rates of chelated 

lead from insoluble particulate material (PbS) and 

97,842 M Po/erem * » "•"a* 

the removal of lead bound to the surface of plant 

material by washing with EDTA. 

Effects of Mine-Mill Comptexet on Stream Biota 

The amount and variety of producer organisms 

vary remarkably from one stream to another. In 

some locations, seasonal algal bloom* have reached 

problem proportions, especially below the confluence of mine-mill wastewater and the natural receiving stream. In some cases, unsightly conditions have 

been created for several miles downstream due to 

unusual and dense algal bloom communities that 

Betjfr. wosh with 

002SM EDTA pHTS 

FIGURE 7-32—Uptake and release 

300 400 500 

ml throuoje- column 

ot lead from eutoclaved culture after washing with EDTA. 

189 
TABLE T.29.-Reteett of ASARCO smelter concentrate Into Bb> Creek 

Sediments measured after acddentil rcreaje of concentrate 

Element u*J% (image) 

Zn Ca 

N. Ditch on Co. Prop. 

S. Ditch on Co. Prop. 

1 mi upstream of effluent 

250 yards downstream ot effluent 

Sempte location 

N. Ditch on Co. Prop. 

N. Ditch on Co. Prop. 

S. Ditch on Co. Prop. 

Stream gist above effluent 

N. Ditch on Co. Prop. 

N. Ditch on Co. Prop.-FEltered 

S. Ditch on Co. Prop. 

S. Ditch on Co. Prop.-PIIrered 

Above eft. smelt Glover - - -

Above eff. smelt Greet 

Below smelt eff. Glover 

Below smelt eff. Glover 

Pb 

• 3.667 

75.167 

10.496 

ISO 

0.14 

0.073 

2 

1 

<0.005 

0.007 

0.03 

0.014 

80.000 

116.000 

10 

1.720 

14.250 

95.000 

32 

650 

Two weeks sfter first notice of release 

Zn 

10.467 

6.933 

37,733 

I6fl 

Element *g/g (enrage) 

Co 

2.546 

1,740 

721 

20 

Weter (unfutered unless marked *ig/g) (average) 

0.41 

0.32 

61 

56 

<0.0I 

0.017 

<0.0I 

<0.0I 

<0.0I 

<0.0I 

0.027 

O.Oli 

<0.01 

<0.01 

<0.0I 

<0.0I 

3.350 

2,200 

10 

64 

Cd 

51.833 

31.000 

203 

I I 

0.034 

0.046 

23 

22 

0.0014 

0.0024 

0.0076 

0.0O62 

3.300 

3.900 

OJ 

290 

Mn 

753 

626 

2,007 

941 

arm 

0.016 

1.27 

0.03 

<0.01 

0.041 

OO) 

odically washed the plant down to control dust. 

Water from the sprinklers drained into the ditches 

on the north and south sides of the plant; during 

periods of storm runoff, materia] from the ditches 

was unintentionally washed into the streams and 

deposited in the sediments. This smelter does dustsmelting and processes concentrates from mines 

elsewhere in the world as well as from the New 

Lead Belt; this accounts for the very high cadmium 

values found along with those for lead, zinc, and 

copper. Although control sedimentation ponds have 

now been constructed to treat the plant runoff, this 

event does emphasize that care must be exercised to 

contain heavy metals and prevent their reaching 

streams. 

Lead in Lake Sediments 

Most mill and mine waste waters in the New Lead 

Belt ultimately How into one of two major receiving 

streams, Logan Creek and Black River. Logan 

Creek receives wastes and mine water from only 

one mine, while the Black River receives the majority of wastes and mine water from the five mining 

operations. The velocity patterns of these streams 

are such that fine particles do not settle; instead, 

they are carried along by streamllow until quiescent 

conditions are found. 

Both Black River and Logan Creek flow into 

Clearwater Lake, where retention times are favora166 _. 

He for sedimentation. The lake is located at Piedmont, MO, approximately 30 mi from the last of the 

Ave mine-mill discharges on the Black River and 

approximately 23 nri from the single mine discharge 

on Logan Creek, (fig. 7-28) In addition to the two 

arms of Clearwater Lake that receive mine-miO 

wastewaters, a third arm receives flow from Webb 

Creek. This stream drains the same forest area, but 

it is not exposed to any type of mining waste products. 

Sediment samples were taken from various parti 

of Clearwater Lake using conventional dredging 

methods and by scuba divers utilizing hand collection devices. These, together with selected samples 

of aquatic biota, were analyzed to evaluate the extent of trace metal accumulation after approximately 

8 years of mining operations. 

Lead concentrations in the lake sediments range 

from less than 3 pg/g at points of stream entry to 

more than 60 jig/g in deeper waters near the dan). 

Zinc and copper concentrations follow a similar 

trend, ranging from 10 to 84 Mg/g and 5 to 30 <-g/g, 

respectively. Cadmium reaches detectable levels (0.3 

to 0.5 Mg/g) only in samples collected near the dam. 

In general, lakes with long narrow arms like Clearwater, are subject to hydraulic scour and washout 

during storms. Under these conditions, sediments 

are swept up and carried toward the discharge tube 

located in the base of the dam. When the tube gate 

is opened to permit discharge from heavy inflows, 

L sediments and associated heavy metals are apt to 

C Rushed from the lake, thus moving out of the 

jcosystem. The relatively low concentrations of 

Uvy metals in sediments near the dam strongly 

West that this flushing action has been an active 

Jjocess, and it will probably continue to be so in the 

itture. Clearwater Lake appears to be a relatively 

tort-time sink for heavy metals. The length of resifcney undoubtedly depends upon the magnitude of 

.ormflows in and out of the impoundment. 

Total body lead content of bluegills, bass, gogglerres, catfish, and minnows collected in the lake 

ange from undetectable levels to 14 Mg/g- The mums membranes of skin and gills show a particular 

affinity for heavy metals. Lead concentrations in 

in, and scales range from undetectable levels in 

affish to 21 »ug/g in bluegill. Gills from a variety of 

fch demonstrate lead content of 5 to 18 Mg/g. Catfish 

•3b generally contain less lead than those of blue-

•31. Freshwater mussels have total body lead i xjneentrations of 23 to 30 Mg/g, most of which was in the 

tnells. Soft internal tissues (muscle, heart, kidneys, 

pstrointestinal organs, and reproductive organs) do 

M have detectable quantities of lead. These data 

alow some interesting comparisons with similar data 

collected from-areas of-much higher-heavy-metal 

concentrations in the mining district. (39) 

There is little evidence that surface mineralization 

ia the mining area has elevated levels of the lead, 

line, and copper. Data from the Webb Creek arm 

ire very consistent, ranging from 13 to 22 mg/1 for 

lead and zinc; these are the norma) background levels expected for New Lead Belt control streams. 

Logan Creek is only slightly higher, ranging from 12 

to 40 mg/1 lead. Values from the Black River arm 

ve far more erratic, ranging from 10 to 64 mg/1 for 

lead and zinc, with most minimum amounts above 

13 mg/1. This arm is more subject to washout than 

(he others, since it drain the largest area. Based on 

GonMotinon from 

SMrna-MlH 

research evaluations of water, sediments, and selected biota, it appears that under present conditions no 

acute toxicity problems exist in Clearwater Lake. 

Limited data on similar streams in Wales (60] and 

Missouri [61] indicate that lead may not be as great 

an environmental hazard as zinc. 

AQUATIC BIOCONCENTRATtON OF METALS 

The release of finely ground rock particles and 

some vagrant mineral particles from the tailings 

ponds is greatest during storm periods, but these 

materials accumulate in the benthos to a greater extent under less turbulent conditions. The magnitude 

of silt accumulation varies and may be complemented by additional precipitation or coprectpitation of 

dissolved minerals as Industrial effluents mix with 

natural surface waters. The accumulation of silt has 

on occasion seriously altered normal stream communities. The turbulence of storm water flows frequently resuspends and redistributes stream sediments. Studies by Jennett and Hardie [44] have assessed the heavy metals content and distribution patterns in the sediments of receiving streams and 

lakes, as well as in the tailings treatment system. 

. The. capacttyof local producer organisms, living or 

dead, to trap and concentrate vagrant heavy metals 

has been observed In both terrestrial and aquatic 

environments. [62-65] In the aquatic environments of 

the New Lead Belt, quantities of lead associated 

with aquatic vegetation have exceeded 74,000 Mg/g 

(dry weight) at the point of mine water discharge, 

and more than 8,000 Mg/g at the discharge of some 

tailings ponds. In both aquatic and terrestrial situations, the degree of heavy metal contamination of 

vegetation decreases with the distance from the 

source. Utile is known about the eventual fate of 

such heavy metals over relatively long periods of 

time. 

RGURE 7-28.—lead corx»ntt>tion rn Ctsarwatvr Lak* .swdbTMnt*. 

167 

CO 
*;• • 

ii. 

£ 

I 

tems is good, the possibility must be considered that 

residual milling reagents in the effluents may contribute to the sparcity of many consumer organisms. 

Toxicity of Milling Reagents 

The toxicity of the various reagents utilized in the 

ore milling process is neither fully understood nor 

appreciated. Persistent identifiable odors and the 

appearance of froth in the final industrial effluents of 

some operations provide clues to the possible reasons for serious changes in aquatic communities 

downstream from the point of discharge. Unfortunately, few data are available on the toxicity of milling reagents to aquatic organisms, and even less is 

known about the actual concentrations of residual 

reagents in industrial effluents. The various 96 h 

median toxic limits, as determined by Hawley [39], 

the U.S. Department of Interior Fish Pesticides 

Laboratory, and Gale [61) are summarized in table 

7-33. These data indicate the range of concentrations 

in which a 30 percent mortality of the test organisms 

occurred. More precise determinations are difficult, 

since considerable variations may be observed from 

one group of organisms to another, depending on 

age, nutritional state, season, sex, water hardness, 

etc. These data are additionally prejudiced by the 

obvious shortcomings of short-term static toxicity 

studies. They offer little information regarding toxicity under conditions of continuous flow, long-term 

effects, nor embryoiogical or teratogenic effects. 

Despite these deficiencies, the results provide an 

approximate comparison of relative toxicity. 

Many of the reagents tested have absorption maxima in the ultraviolet range, but the extinction coefficients are often too small to permit detection at the 

very low concentrations known to be toxic to aquatic organisms. [70] The lack of adequate analytical 

techniques has been a serious factor in determining 

concentrations of milling reagents at various points. 

in the mill circuit, in the tailings ponds, or final tailtngs effluents. Some of the reagents remain bound to 

the mineral particles and thus never enter the tailings. Other may not bind to ore particles, but remain 

in the final tailings. In mills that use a copper circuit, 

the addition of SO2 to separate the lead and copper 

minerals may, under certain conditions, also cause 

the release of considerable quantities of xanthate 

collectors; these may be detected in the thickener 

overflows. Degradation rates vary considerably [71] 

and may be affected by pH, temperature, or redox 

potential. 

Addison et al. [72], working in New Brunswick 

with mill effluents from sulfide ore, identified xanthate residuals of 0.2 to 1.2 mg/1; dithiophosphate 

residuals from 0.3 to 2.7 mg/1; and isopropyl ethyithionocarbamate residuals of 1.8 mg/1. Limited analyses of effluents from a New Lead Belt mill process 

found xanthate concentrations of 0.3 mg/1 in thickener overflows, but undetectable levels (less than 0.1 

mg/1) in the final effluent. Long-chain alcohols have 

been determined to exceed 200 mg/1 in the final 

effluent on one occasion, and at another time were 

undetectable (less than 10 mg/1). 

More detailed data are needed relative to the final 

effluent concentrations of these toxic substances. 

Circumstances that would permit toxic concentrations of milling reagents to enter receiving streams 

should be eliminated. In those situations where 

problems exist and mill effluents are suspect, every 

precaution should be taken to ensure adequate treatment of tailings and effective isolation of effluents 

known to contain toxic levels of reagents. Where 

possible, reagents should be selected on the basis of 

favorable degradability properties or reduced toxicity. 

TABLE I-Ji.-Taxldty ofvariousmining reagents, 96Ji median toxic limttt' 

Reagent 

Methyl bobutylcarbinoi 

Propylene glycol 

methyl ethers 

Long-chain aliphatic alcohols 

Potassium or sodttim 

•my l xanthate 

Sodium isopropyl 

xanthate 

Sodium ethyl 

xanthate 

Isopropyl ethyl 

thktnocatb.mate 

Sodium diethyl* 

dithiophosphate 

Minerec B 

(dixanthogen) 

Aero-130 

(thkrcarbanatrde) 

Fathead Emerald Water 

minnow shiner fleas 

IOO-1.000 

> 1,000 

100-1.000 

1.8 -18 10-100 0.1-1.0 

0.18-IS 0.01-0.1 0.1-1.0 

0.18-1.8 0.014.1 0.1-1.0 

10-100 

- 0.1-1.0 

_ 

-

BtaegiQ 

— 

>1,00 0 

50-100 

100.200 

0.0141.1 

10-100 

10-50 

660-1,000 

1.0-10 

>i.ono 

Catfish 

— 

_ 

10O-500 

_ 

>10 

_ 

10-100 

_ 

_ 

-

Snafls 

_ 

100-500 

100-1,000 

1.0-10 

10-100 

100-1.000 

10.100 

> 1.000 

100-200 

100-1.000 

Tadpole. 

_ 

-

10-100 

_ 

10-100 

_ 

_ 

_ 

_ 

-

Crayfish 

600-1.000 

>10 0 

10-100 

100-200 

1-10 

100-500 

100-200 

_ 

_ 

-

Golden 

shiner 1 

_ 

-

<23 

_ 

_ 

_ 

_ 

_ 

_ 

-

Algal 

photosynthesis 

_ 

_ 

100-200 

100-200 

10-100 

100-200 

100-200 

_ 

_ 

-

1

 Data on fathead minnows, emerald shiners, and water fleai from Hawley [681. on catfish from U.S. Department of Interior Fish 

Pesticide Laboratory (Columbia, MO); remainder by Gale 1391. 

172 

'summary 

L

Under present conditions, lead and other disIved heavy metals do not present a significant biojtogica) hazard to aquatic organisms of the New Lead 

;Belt. (Zinc may be an exception and is still under 

Jdudy.) This fortunate circumstance is the result of 

!tte alkaline pH and the elevated hardness characteristic of the surface and subterranean waters of the 

legion, combined with pollution control procedures 

initiated by industry. 

Aquatic vegetation within the various mine-mill 

treatment systems and in the receiving streams is 

efficient in trapping and binding heavy metals that 

may be present in the particulate material entering 

ihe water. Most of the heavy metals accumulated by 

tlgae or other aquatic vegetation appear to be bound 

10 the surface of the plants and may be removed by 

washing with solutions such as EDTA. Aquatic vegetation is only a temporary host for the metals, since 

they are carried downstream during storm runoff 

periods. 

Suspended solids in streams are a major transport 

mechanism for heavy metals. These heavy metals 

originate from smelters, mine-mill tailings ponds, 

tod tailings dams, or directly off contaminated soil. 

Most of this transport occurs during periods of storm 

runoff, when the soil and leaf litter are washed into 

the stream, and the treating ponds are subjected to 

turbulence. Since streams in the region contain very 

jfittte fine sediment and clay, most of the heavy metals are transferred out of the New Lead Belt ecojtystem. 

Clearwater Lake is the only long-term impound1 merit in which heavy metals can accumulate to any 

extent. Research indicates that heavy-metal levels 

ve increasing, but do not present a problem under 

existing conditions. Since this lake is subject to 

flooding that results in resuspension and flushing out 

I of sediments, it should not be considered as a permanent sink for heavy metals. 

Analyses for heavy metals within the tissues of 

1 normal consumer organisms have not indicated any 

significant biomagnification of lead, zinc, or copper. 

j Total body content of these heavy metals is considerably more elevated in consumer organisms near 

1 tsitings dams or within the treatment systems than 

| (or those in control streams. Research indicates that 

I present metal levels do not represent a serious hazard to streams in the New Lead Belt. Game Ash are 

1 common within the tailings ponds and meanders of 

[ some mine-mill operations where the aquatic vegetation is heavily laden with lead and zinc. 

The ore concentration mill, with its attendant process reagents and finely ground tailings, represents 

the greatest concern for the aquatic ecosystem. Control must be maintained through adequate tailings 

systems for the neutralization of toxic chemicals and 

the removal of fine particulate matter. The elimination of toxic chemicals and effluent particulate matter from the final tailings pond effluents would ensure minimum adverse effects from the industrial 

operations on the receiving stream. In addition, it 

would control the release of heavy metals (as particulates), which is not a major problem under present 

conditions. Research should continue for the development of better analytical methods to detect organic milling reagents found to be toxic to stream organisms. 

REMOTE SENSING AND DATA PROCESSING 

The Missouri lead-belt study provides an excellent 

opportunity for the utilization of remote sensing 

techniques; and because of the large size of the 

sampling program, new techniques for data processing and presentation were developed. The results of 

these investigation arc briefly described below. 

Remote Sensing 

The primary objectives of the remote sensing efforts were to develop effective technloue* for remotely sensing heavy-metal concentrations m soil 

and vegetation and to develop efficient image processing techniques for detecting the effects of trace 

metals in the environment. This ia a mature technology, [73J and undoubtedly success could be achieved 

using the highly sophisticated multichannel data 

collection and optimal data processing techniques 

currently available. The project objective, however, 

was to determine the degree of success that could be 

achieved by using inexpensive 4-ehannel multispectral photography, a technique easily within the reach 

of local industries and agencies. 

In order to produce preliminary results in a reasonable period of time, the frtitloj study area was 

limited to an area 10 km by 10 km, centered on the 

AMAX lead smelter near Boss. MO. Ground truth 

consisted of approximately 250 toil samples and 110 

vegetation samples obtained in this area. These 

samples were interpolated using a linear interpolation algorithm [74] to form spatial distribution for 

the soil and vegetation. The spatial distribution, with 

the resulting contour maps for copper, lead, zinc, 

and sulfur concentrations in soil, are shown in figure 

7-35. Vegetation samples yielded similar distribution. 

The techniques for developing these distributions 

will be briefly discussed. 

The study area was overflown twice during the 

spring (May 17) and fall (Oct. 5) of 1973. A Hasselblad 70 mm, 4 camera cluster, operated by the University of Kansas Center for Research, Inc., was 

used to obtain imagery in the blue, green, red, and 

near-infrared bands. The camera array and aircraft 

mounting are illustrated in figure 7-36. Film specifications are given in table 7-34. Each mission consisted of one flight at an altitude of 11,000 ft using a 

wide-angle 40 mm lens and one flight at 6.000 ft using a 100 mm lens. High altitude coverage using a 

wide-angle 40 mm lens was desirable to prepare an 

image mosaic covering the area of interest, since 

with fewer frames to splice, higher geometric fidelity 

is obtained. In return for this coverage, resolution is 

sacrificed. The low-altitude coverage obtained highresolution imagery for identification and mapping 

purposes. 

173 
If.: 

become coated with associate gangue. In some instances, this increased productivity has encouraged 

the production of game fish. Studies on the environmental impact of seepage from a century-old tailings 

pile in the Old Lead Belt of Missouri indicate that 

sediment and biota contain elevated amounts of zinc 

due to stream contamination. [69] 

Figure 7-33 shows the schematic of the tailings 

ponds and meander system installed below the 

AMAX Buick mine and mill that produce lead and 

zinc concentrates. The principal milling reagents 

employed are shown in table 7-30. This table illustrates differences between mills employing a copper 

circuit in the flotation process. Since completion of 

the meander system and final settling pond, this operation has successfully eliminated most nuisance 

algal blooms in the receiving stream and has 

markedly improved retention of particulate material 

and heavy metals within the system. [54] 

Growth of aquatic vegetation within the meander 

system and final settling pond effectively traps and 

binds most of the vagrant mineral particles released 

from the tailings lagoon, and the overall retention 

time in the system permits effective degradation or 

dilution of any remaining milling reagents. Aquatic 

-vegetation at the head of the meander.system normally displays lead contents of several thousand 

parts per million; these values drop to a few 

hundred within tbe fnal settling pond. 

Normal consumer organisms—including aquatic 

insects, snails, tadpoles, crayfish, WuegHls, bass, 

carp, and catfish— abound in the lagoons and meanFL0TATI0N 

TABLE l-lO.-Princtpat mttUng reagents employed at 

New Lead Belt flotation processes 

Reagent 

AMAX-Buick mill 

(no copper circuit) 

Fletcher mine-ma 

(with copper circuit) 

Zfticdaprexsant 

Zinc activator 

Iron depression 

and pll control 

Lead depression 

and rapper 

dotation 

Methyl tsobulyl. 

carbinol propylene, and 

pry col-methyl ethers 

Sodium diethyldithiophn<.phate and 

lodium isopropylelhylthionocarbainate 

Sodium ethyl xanthate 

ZnSO, 

CuSO. 

Lime 

C.-C. aliphatic 

alcohols 

Sodium fsopropylethylthiono* 

carbamate 

Sodium bopropyl 

xanthate 

ZnSO, + cyanide 

CuSO. 

Caustic soda 

SO, + itardi 

ders. Total body analyses for heavy metals in the 

larger consumers reflect the high content of metals 

in consumed -vegetation and- mucous- coverings of 

insect larvae that comprise a major part of the diet 

of higher trophic levels. Considerable quantities of 

lead and zinc are found in the gills, mucous membranes, and bones of fish, (tables 7-31 and 7-32) The 

fleshy portions of fish likely to be consumed by 

humans are relatively free of heavy-metal contarmLEAO-ZINC GRINDING I 

ORE FROM J U(l l l i 

MINE ^ _

M|LL

_I 

WATER 

PUMPED 

FROM 

MINES 

EXCE3S WATER 

TOURE 7-33.—Schematic of the tellings ponds and 

-170— 

tystem talow tht AMAX Butck mint. 

TABLE 7-3l.-fff.wy metals In fah. mSIA 

li-atwn/fWi part Pb litxJt) Zn tufjg) Cu UtsJt) 

Tadpoles from meander. 

I0O yards down meanders 

Eviscerated body 

Intestine and contents 

U Cave Hollow Junction 

l>er and heart 

Eviscerated body 

Intestine and contents 

Total body 

213 

4.419 

256 

2.926 

22 67 

93 240 

7.329 4.696 

4,139 2.808 

20 

234 

260 

169 

Bhjegllh from meanders 

Muscle 

Bone 

Skin and scales 

Intestine and contents 

Gills 

Total body 

104 

132 

390 

161 

84 

45 

152 

229 

381 

109 

157 

53 

19 

24 

Bass from meanders 

Muscle 

Bone 

Skin and scales 

Intestine and contents 

Gills 

Total body 

< l 

142 

194 

259 

160 

7 

30 

89 

176 

279 

105 

117 

13 

22 

27 

159 

24 

Bluegjtb (fatal tailings pond-spring) 

Mtnde.bone.xktn, 

•nd scales 

Intestine and contents 

Washed intestine 

U rn 

Ovaries 

Gi3b 

Total body 

20 

626 

9 

<1 

<1 

52 

50 

82 

437 

77 

83 

98 

93 

100 

7 

37 

13 

12 

8 

7 

Btnegilb (final tattings pond-nntmer) 

Muscle 

Bone 

Skin and scales 

Intestine and contents 

GtlU 

Total body 

IS 

22 

30 

38 

32 

42 

77 

121 

61 

82 

20 

14 

20 

nation, since most of the heavy metals actually are 

contained in fecal matter within the intesttonal tract. 

Heavy-metal contents of the intestines and gills vary 

seasonally, reflecting climatic conditions and differences in species diet. There is no evidence of significant food chain concentration of heavy metals in the 

higher trophic levels of aquatic communities. 

A schematic for the mine and mill tailings and 

recycling system at the St. Joe Minerals Corp. 

Fletcher Mine and Mill is shown in figure 7-34. This 

operation produces lead, zinc, and. copper concentrates and has been considerably more confined by 

the space available for tailings treat mem. The principal milling reagents employed are included in table 

7-32. Due to space restrictions and efforts to improve conditions in the receiving stream, this operation has separated the mine and mill wastewaters 

tod is recycling the latter. However, total recycling 

FIGURE 7-34—-Schematic ot New Load Bttt rrtne^ntn recycle 

treatment system. 

of mill wastes has not been achieved due to some 

leakage from the mining wastewater retention lagoon. — -

Growth of aquatic vegetation in the short discharge stream below the final (mill) tailings pond has 

been limited to seasonal blooms of blue-green algae, 

diatomaceous mats, and a few pond weeds. Development of aquatic vegetation in the stream receiving 

the Fletcher operation discharge has usually been 

depressed in the early spring, as compared with other control streams or the same stream above the 

point of effluent discharge. Normal aquatic communities have been replaced by dense diatomaceous 

mats during the summer months, especially under 

low-flow conditions. Relatively high manganese content, along with other residua) milling reagents m the 

effluent, has been cited as one possible contributing 

factor to the unusually dense diatom populations and 

exclusion of the normal aquatic growths. 

Dominant aquatic consumers in the New Lead 

Belt area include minnows, sunfish, and bass. Other 

consumer organisms common to these Ozark 

streams—such as snails, crayfish, tadpoles, and various aquatic insects—are extremely rare or missing. 

Since heavy-metal retention within most tailings sysTABLE Vn.-Heavy metals fc/ftn, mfflfl 

Fhhpert 

Mascte and bone 

Gilts 

Intestine and contents 

Her e end bone 

GUK 

Intestine end contents 

Tola] body 

n> ba/g> zn lain c° (ug/g) 

Stilling pool: bhjcgflb 

17 91 2 

28 90 2 

22 151 10 

Final eflhtent: tjteegills 

<1 90 3 

<l 80 1 

<l 81 6 

6 165 } 

171 
TABLE V36.-Correlatlon coefflcientt-smgle color band 

(single color band-vegetation ground truth) 

fe 

1 

I 

I 

Ground troth 

Post oak (read) 

Pott oak (sulfur) 

Pine needles (lead) 

Pine needles (sulfur) 

Post oak (lead) 

Post oak (sulfur) 

Pine needles deed) 

Pine needles (nilfur) 

Post oak (leed) 

Post oak (sulfur) 

Pine needles (lead) 

Pine needles (sulfur) 

Post oak (read) 

Post oak (sulfur) 

Pine needles (lead) 

Pine needles (sulfur) 

Color band 

Infrared 

Infrared 

Infrared 

Infrared 

Red 

Red 

Red 

Red 

Green 

Green 

Green 

Green 

Blue 

Blue 

Blue 

Blue 

Hay 17 

0.303 

-0.109 

0.330 

0.163 

-0.(109 

0.138 

- 0.359 

0.224 

0.126 

0.O9I 

- 0.068 

0.052 

0.177 

0.228 

0.083 

0.183 

p 

Octobers 

-0.080 

0.045 

0.096 

-0.017 

0.368 

0.139 

0.J01 

0.342 

0.165 

0.090 

0.333 

0.214 

0.055 

0.169 

0.231 

0.059 

adequate computer systems, are available. The spatial displays illustrated were generated with a CALCOMP platter with an IBM 3601/65 computer. In 

addition to the program for generating the spatial 

displays, techniques have also been developed for 

generating contour maps directly from field data. 

[76] 

The routines for generating spatial displays and 

contour maps involve the process of interpolating 

field data to generate artificial sample values; 

through the use of these interpolating routines, sample values can be estimated. Statistical tests may be 

used to estimate the accuracy of these artificial samples, and if this accuracy is sufficiently high, field 

samples can be eliminated or collected at a point 

that win yield more meaningful information. The use 

of these techniques has been documented, and the 

results show that a potential exists for significantly 

reducing the cost of a field sampling program by 

reducing the required number of field samples for 

area parameterization. (77] 

CONCLUSIONS 

Comprehensive studies in the New Lead Belt of 

southeast Missouri have (I) investigated the movement of lead and other heavy metals from mining, 

milling, and smelting operations through, and out of, 

the surrounding forest ecosystem; and (2) determined the impact of these heavy metals on environmental quality. Two principal source-to-sink routes 

have been identified from these operations. 

Smelting operations are a source of concentrates 

and stack emissions containing heavy metals. Fugitive dusts, which are moved by wind and deposited 

on the surrounding vegetation and soil, are the major source of contamination within 3 mi of the smelter. Beyond 3 mi, stack emissions are the predominant source as airborne particles that are discharged 

and gradually settle to tne earth, carrying along associated heavy metals. 

178 

Mining and milling operations are another major 

source of heavy metals. Finely ground materials 

from the tailings dams or concentrate piles are windblown into the forest or wash directly into recrivrnj 

streams. 

The transport of finely ground ores and conceiy 

trates from mines and mills to the smelter provide, 

another source of contamination within the ecosystem. When materials are transported in open trucki 

and railroad cars, considerable amounts are blown 

away and deposited on adjacent vegetation and soil. 

Although concentrations of lead can be quite high 

adjacent to the roadways, levels approach background within a few hundred feet of the haulage 

roads. 

Lead and other heavy metals that are deposited on 

the forest floor tend to concentrate in the organic 

layers, with very little moving into the underlying 

mineral soil horizons. Geochemical analyses of leaf 

litter appear to be a much more sensitive means of 

evaluating the extent of pollution than are air quality 

measurements. 

Although large quantities of lead have accumulated in the organic soil horizons near smelters, there 

appears to be little danger of movement downward. 

Soil, particularly the clay and organic fractions, 

have a strong affinity for lead and effectively prevent 

its downward movement. 

The accumulation of lead by vegetation, especially 

vegetables and forage crops consumed by humans 

and animals, is a considerable cause for concern. 

The greatest accumulations are near smelters or hi 

areas where crops are grown on soils near ok) mines 

or on soils that have been amended with dotornitic 

limestone mine wastes. The deaths of several horses 

grazing near a smelter have been attributed to lead 

poisoning. 

Storm runoff is the major transport mechanism in 

the movement of lead. Evidence indicates that 

heavy metals do not concentrate in stream sediments, but relatively large amounts are carried by 

suspended solids associated with stormflows and 

temporarily deposited downstream in Clearwater 

Lake. Heavy metals are accumulating in the lake 

sediments, but research indicates that most of the 

metals are carried out of the lake during storms and 

do not pose a problem under existing conditions. 

The transport of lead by stormflows may well Emit 

its accumulation in the ecosystem. Present evidence 

suggests that lead levels in the New Lead Belt, 

which is only 6 to 8 years old, are approaching those 

found in the Old Lead Belt, where operations have 

existed for about 100 years. Thus it is likely thtt 

accumulations may stabilize within a few years. 

Data from soil and vegetation studies show thtl 

smelting operations produce greater heavy-mets! 

anomalies in terrestrial systems than do mining and 

milling operations. Within aquatic systems, however, 

the mine-mill complexes are the major sources of 

contamination. Aquatic problems in the New Lead 

Belt have been ameliorated by fortuitous stream 

characteristics. The alkaline reaction of natural waters retards the solubilization of the predomiriantly 

[cad sulfide ores. In time, problems could arise from 

[ihe more soluble forms of lead in smelter emissions. 

It is entirely possible that zinc may cause more 

problems than lead in aquatic environments. Also, 

|tbe organic reagents used in milling operations, some 

of which are quite toxic, may be environmentally 

iunaging. In addition, some of these reagents have 

reduced excessive algal blooms and growth of diatomaceous mats. Although unsightly, these aquatic 

Ipowths have trapped large quantities of lead and 

other heavy metals. This characteristic has been utilized in the development of meander systems designed to enhance the quality of water released from 

lutings ponds. 

Recommendations for pollution control and research application have been utilized where possible 

by industries and agencies for various aspects of air, 

nQ, vegetation, and surface water in the New Lead 

Bdt of southeastern Missouri. 178) 

A technological and cooperative approach must be 

contimied between industry, regulatory agencies, the 

engineering and scientific community, and the generi public if mineral resources are to be produced 

wihout a detrimental environmental impact. 

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NSF-RANN Trace f"ifaiT'''*«w*T Ctonferenot. AsOomar, CA 

(1974). 

21. Ecology and AiwJysss of Trace Ccrts-ntaaws, Progress Report (or Period October 1973 - September 1974. ORNL-NSFEATC1I. Oak Ridge National Ubontory, Oak Ridge. TN 

(1974). 

22. A.P. Watson. Trace Ekanent bnpact on Forest Floor Utter ks 

the New Lead Bdt Region of sootJwastern Missouri. Proceedings of 9th Anraskl Conference, on Trace Substances in 

Envbutinwrttal Health, University of Missouri. Orfumbta, 

MO (1975). 

23. D. DpaSc. A. Kerin, L. Gmmsc-Lepowvte, L, Novak, end S. 

Kop. Arch. Environ. Health. 23:273 (1971). 

24. J. Sctunifl. G. Brown. E. Devlin. A. Lassen. fc. MrTanshmfl, 

and J. Seville. Arch. Environ. Health. 23:185 (1971). 

23. O.T. C<oodmen and T.M. Roberts. Nature. 231:287 (1971). 

26. H.L. Cannon end J.M. Bowles. Science. 137 763 (1962). 

27. R.H. Dames. H. J. Mono, and DM . Qtillo. Environ. Sd. 

Tectmol. 4: 318 (1970) qU.V. I iii*,. . ft and A.W. Specht. 

28. J. V. Lagerwerff and A. W. Specht. Environ. Sci. Tectmol. 4.583 

(1970) 

29. A J. MacLead. R.L. Hsistead. and BJ. Hno. Can. J. Sou 

Sd. 49: 327 (1969). 

30. H.L. Motto. R.H. Dates, D.M. CbJfto, and C.K. Motto. 

Environ. Sd. Techno.. 4 231 (1970). 

31. W.H. Smith. For. Sd. 17:195(1971). 

32. A. Haney, J. A. Carlson, snd OL. Rolfe. Trans. ID. Acad. 

Sd. 67:323(1974). 

33. JJ. Corner. H.T. Shacktette. snd J.A. Erdman. USDS . 

pRfosional Paper. 750-B. BI3I. (1971). 

34. Bolter, E. In An Intetdistipfaary Investigation of Environmental Mlution by Lead and Other Heavy Metals by Industrial Development m the New Lead Belt of Southeastern 

Missouri, vol. 2, B.G. Wixson and J.C. Jennett. ed. Annual 

report submitted to NSF-RANN by the University of Mhv 

souri-Ro(la(l974). 

35. D. D. Hemphill. C. J. MsrierfeW. R. S. Reddy. and J. O. 

Pierce. Arch. Environ. Health. 28: 190(1974). 

36. D. D. Hemphill. C. J. Marienfeld. R. S. Reddy. W. D. Hesdtage. and J. O. Pierce. J. Ass. Offlc. Anal. Chem. JeV 994 

(1973). 

37. An Interdisciplinary Investigation of Envsronmental Pollution 

by Lead and Other Heavy Metals by Industrial Development 

in the Lead Belt of Southeastern Missouri. 2 vol. B. G. Wixson and J. C. Jennett. ed. Annual report submitted to NSFRANN by the University of Missouri-Rotta. (1974). 

177 
•!•'. 

r 

& 

I: 

it 

51K' fe 

P.H. 

FIGURE 7-M.-8p«1l*l distributions and contour mape for aoil 

TABLE 1'iA,^/tasselblad camera fum specification! 

Image band (nm) Filter (Kodak) Film (Kodak) 

Blue (400-500) 47 B 

Green (500400) S8 

Red (600-700) 2J 

Infrared (700*900) 89 B 

BAW 2402 (Ptos-X Aero) 

BAW2402 

B A W 2402 

IR B 4 W 2402 (Infrared Aero) 

Examination of the imagery indicated Ihal the red 

band was Ihe most suitable in terms of image contrast and reflectance variations across an individual 

frame due to incidence angle differences. Atmospheric scattering effects limit the contrast quality of 

the Hue band. The same effect is also resrxmabte 

for the low contrast observed near the edges of the 

(b) Ctoaeup of camera mount 

174 

••ten band frames due to increased atmospheric 

JBB53 at these angles. In the case of the infrared 

[and. atmospheric scattering is negligible. The target 

,ef)ectance, however, appears to be sensitive to incidence angle, thereby causing difficulty in making a 

ifosaic of adjacent frames due to differences in 

density levels. Although the red band mosaic possesses the best qualities, all four bands were used in 

the color-combination and correlation studies. 

Two techniques were used for data analysis and 

interpretation. First, color-combined mosaics were 

pnerated and compared visually with the groundnut!, contour maps. Then, correlation coefficients 

sere generated between each set of ground-truth 

data and each color band. 

The color combiner consists of three slide projectors positioned in such a way that their beams, upon 

reflection by a mirror, are superimposed on a ground 

jkss screen. Each of the beams is passed through 

one of three color filters: blue, green, .or red. Furtfarnore, the intensity of each light beam can be 

controlled. Hence, by inserting three slides of a given scene corresponding to the same or different 

spectral bands, the color combiner win produce a 

color image of the three original black-and-white 

images. ... _ __ _ . .. 

About 40 different false-color images were produced and analyzed. Although some of these new falsecolor images greatly enhanced tbe discrimination 

between different terrain features, visual inspection 

revealed no apparent correlation between patterns of 

(be false color images and the metal concentration 

maps. This technique was consequently used on the 

imagery from the first flight only. However, color 

combining was quite successful to discriminate between different features in the tailings pond. The 

resulting false color displays allowed the field engineers to efficiently select pertinent sampling sites. 

Mapping of surface features and area parameters for 

water, wooded areas, fields, and cultural features 

was also successful. 

The correlation studies were performed using the 

IDECS (Image Discrimination, Enhancement, and 

Color Combination System) at' the University of 

Kansas. First, the image mosaic from each mission 

was quantized and compressed into a 64 by 23 array. 

(The aerial photography covered the entire northtouth extent of the 10 km by 10 km nwtal-concetv 

tration area, but only about one-third of the eastwest width.) The 64 by 23 image array mapped onto 

rows 1 through 64 and columns 26 through 48 of the 

metal concentration array. With the two arrays 

quantized and registered, they were then cross-correlated. 

Upon examining the preliminary result of crosscorrelating the complete arrays, no discernible pattern was apparent. AH factors that could have possibly led to this result were then eliminated. These 

include extrapolation of ground data to form the 10 

km by 10 km metal concentration maps and quantization of the ground data and the imagery into discrete values. Out of the 64 by 23 image cells, only 

those with corresponding ground data points were 

next considered. Scattergrams of these new paired 

sets were then plotted and correlation coefficients 

calculated using actual concentration and image 

density values (no quantization). Similar scattergrams were also produced between the ground data 

and the density ratio of each of the four bands. 

None of these efforts produced any conclusive results. 

The correlation coefficients between tbe soil and 

air-craft photographic data are given in table 7-3S. 

All correlation coefficients are small, being less than 

0.2 in absolute value. There are. however, several 

interesting observations that can be made. It appears 

that in late spring, blue band imagery and soil data 

correlate best. In early fall, infrared and green correlate best with the soil data. [75] 

In an effort to achieve higher correlation between 

photographic end ground-truth data, the ratios of 

two color bands were taken. Ml ratio tests resulted 

in low values of the correlation coefficient. 

Vegetation data were then correlated with the 

imagery using only held samples and image density 

values (no array extrapolation and no quantization). 

These results are somewhat more encouraging, (table 7-36) They indicate that additional studies are 

warranted. A pemixbation analysis of the sampling 

site locations resulted in rather large changes in the 

correlation. Thus it was felt that the precision used 

in locating the sampling sites was not satisfactory 

for this use, and this segment of the study was discontinued. 

Data PrcKxssstng 

One of the first problems encountered tn the Missouri research project, which collected such a large 

quantity of data, was to establish a display format 

so that large-scale features would be evident upon 

quack examination. This problem was solved by the 

use of spatial data displays as illustrated in figure 7-

32. Such data displays may be quickly constructed if 

. TABLE 1i5.-Corvekft1on coeffklentt-stngle cote band 

(sbtgk color band - soil ground truth) 

Ground troth 

Copper 

Lead 

Zinc 

Sulfur 

Copper 

lead 

Zinc 

Sulfur 

Copper 

Lead 

Zinc 

Sulfur 

Copper 

Lead 

Zinc 

Sulfor 

Color band 

Infrared 

Infrared 

Infrared 

Infrared 

Red 

Red 

Red 

Red 

Green 

Green 

Green 

Blue 

Blue 

Brae 

Blue 

May 17 

0.080 

0.03T 

0.0S3 

0.076 

0.074 

0.060 

0.067 

0.03} 

0.070 

0.061 

0.071 

0.058 

0.154 

0.125 

0.131 

0.128 

p 

Octobers 

-0.170 

-0.139 

-0.149 

-0.136 

-0.061 

-0.074 

-0.069 

-0.003 

-0.174 

-0.163 

-0.181 

-0.080 

-0.091 

-0.054 

-0.068 

-0.093 

ITS 
•ft" I: f 

it. 

*••( , 

i 

I 

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water. 13th ed. Americsn Public Health Association, Wash-

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age Works. IM: 471 (1967). 

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2nd NSF-RANN Trace Contaminants Conference. Asilomar, 

CA(I974). 

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by Lead and Other Heavy Metals by Industrial Development 

in the New Lead Belt of Southeastern Mi-souri. 2 vol. Report 

submitted to NSF-RANN by the Umvenity of Miisouri-Rolla 

(1972). 

47. E. Bolter. J.C Jennett. and B. G. Wixson. Qeochemtcal Im-

pact of Lead Mining Waste Waters on Streams in Southeast-

ern Missouri. Transactions of the 27th Purdue Industrial 

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48. N. L. Gale. M. G. Hardie. J. C. Jennett, and A. Aletl. Trans-

port of Trace Pollutants in Lead Mining Waste-waters. Pro-

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port Mechanisms of Lead Industry Wastes. Transactions of 

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Heavy Metals to Protect Aquatic Systems tn the New Lead 

Belt Area. Proceedings of 30th Purdue Industrial Waste Con-

ference, Lafayette. IN (1973). 

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tion in Relation to Automobile and Mint and Smelter 

Sources. Transactions of Seminar on Heavy Metals in the 

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PART III 

Effects of Lead 

a178 

ro 

Ja. 
titta^ 

;V 6.A' 

irri 

t?c 6f I L

- f-4 o

u 

LEAD In The 

Environment A Report and Analysis of neaearch at 

Colorado State University 

University of Illinois 

at Urbana-Champaign 

and 

University of Missouri 

at Rolla 

Prepared for 

The National Science Foundation 

<f"f~wimam R. Boggess. Editor _ V 

Professor Emeritus of Forestry 

University ol Illinois at Urbana-Champaign 

Bobby O. Wixson, Assistant Editor 

Professor of Environmental Health 

University of Missouri at Rolla